CN101133091A - Modified polyolefin waxes - Google Patents

Modified polyolefin waxes Download PDF

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CN101133091A
CN101133091A CNA2006800067077A CN200680006707A CN101133091A CN 101133091 A CN101133091 A CN 101133091A CN A2006800067077 A CNA2006800067077 A CN A2006800067077A CN 200680006707 A CN200680006707 A CN 200680006707A CN 101133091 A CN101133091 A CN 101133091A
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methyl
acrylate
wax
polyolefin
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CN101133091B (en
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D·黑林
B·豪尔
T·普法伊费尔
A·费希特恩考特
H·拉毕格
E·贝克
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/12—Printing inks based on waxes or bitumen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Dental Preparations (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention relates to modified polyolefin waxes carrying (meth)acrylate groups and to a method for the production and use thereof.

Description

Modified polyolefin waxes
The present invention relates to have the polyolefin-wax of (methyl) acrylate group, a kind of their method and their purposes of preparing.
Polyolefin-wax and especially polyethylene wax is known already.These are essentially usually not linearity, hydrophobic polymer with functional group.Yet the functionalized of this polyolefin-wax is useful for obtaining required performance.
Functionalized for example can be by having the comonomer copolymerization of suitable functional group, or by polyolefin-wax with post-modification as by carrying out with the monomer-grafted polymerization that has functional group.
The present invention relates to have (methyl) acrylate group and for example will be used for crosslinked polyolefin-wax.Because female monomer will have at least two polymerisable groups and therefore make polyolefine crosslinked, this polyolefin-wax can not obtain by copolymerization or grafting subsequently.
J.Appl.Polym.Sc., 1993 (48), 167-179, K.B.Ekman, J.J.N  sman and H.Sj  str  m have described ethylene-acrylic acid copolymer and glycidyl methacrylate, ethylene-methyl methacrylate hydroxyethyl ester copolymer and isocyanic ester, and ethylene-vinyl alcohol copolymer and acrylic acid with post-modification with two keys.
Although the shortcoming of the method for modifying of there report is rapid reaction conditions (temperature 190-200 ℃), it only with low yield (with the reaction of glycidyl methacrylate in be not more than 33%, with acrylic acid reaction in be not more than 13%) carry out.Yet this high temperature of reaction causes such risk: acrylate group is with polymerization or cause strong colored product at least.
WO 02/85963 has described by using α, beta-unsaturated carboxylic acid derivatives graft and make the polyolefin modified possibility with special fusion enthalpy.
In long list, especially mention with maleic anhydride or hydroxyalkyl acrylates graft modification.Yet example only clearly discloses and has used modified by maleic acid anhydride graft, and acid anhydride is opened by hydroxyalkyl acrylates in step subsequently.
This produces two shortcomings, the first, modification requires two steps: originate at first polyolefine and maleic anhydride graft reaction, acid anhydride is opened by hydroxyalkyl acrylates then, the second, a carboxylate group of acid anhydride keeps unmodified and hydrophilic radical is provided at acid anhydride and hydroxyalkyl acrylates reaction back.Yet owing to need hydrophobic performance usually under the situation of polyolefin-wax, the inevitable formation of hydrophilic radical has weakened the hydrophobic performance of required product.
(methyl) acrylate is usually by making (methyl) acryllic acid catalytic esterification or base catalysis esterification, or other (methyl) acrylate and pure transesterify and prepare.
Base-catalyzed transesterification or other synthetic generation complex compound and the generation of coloured product mixtures sometimes usually.For removing color and unreacted reactant, must be with product mixtures aftertreatment by complicated alkaline washing.
It is known urging esterification or transesterify to prepare (methyl) acrylate by enzyme.
J.Am.Chem.Soc.2002,124,1850-1851, Kumar and Gross have described the lipase-catalyzed reaction of isopropylidene protection sugar with the methacrylic vinyl acetate.Because the vinyl alcohol that discharges is removed as acetaldehyde from molecular balance, and complete reaction realizes by special starting raw material first class vinyl acrylate.The shortcoming of this method is that the methacrylic vinyl acetate as particular monomers (activation acrylate) is expensive and only commercially available on a small quantity.
Biocatalysis, 1994,9,145-155, A.T.J.W.de Goede etc. described α-O-octyl group-glucoside and ethyl propenoate in the presence of lipase transesterify to form the 6-O-acrylate.The shortcoming of this method be only limit to glucoside and glycosidic linkage and in glucoside to the steric influence sensitivity.In addition, the product of higher acrylated is owing to the secondary reactions of non-selectivity obtains.
EP-A1999229 has described polyoxyalkylene and has urged esterification and transesterify with the enzyme of (methyl) vinylformic acid and (methyl) acrylate.
WO 03/042227 discloses the lipase-catalyzed transesterify of alkyl acrylate with sugar.
Biotechnol.Lett.1990,12,825-830, Hajjar etc. have described and have used the lipase from Chromobacterium viscosum to make ring-type and open chain alkane glycol and ethyl propenoate enzyme urge transesterify.Reaction is carried out in solvent-free system with the alkyl acrylate with respect to 18 times of molar excess of glycol.Form the mixture of mono acrylic ester and diacrylate.
WO 2004/42069 has described polyacrylic ester and (methyl) vinylformic acid that has hydroxyl or (enzyme of methacrylic ester is urged esterification or transesterify.
Yet, compare with polyolefin-wax, polyacrylic ester is the strongly hydrophilic polymkeric substance, make because enzyme has very high base material specificity and enantioselectivity, regioselectivity or chemo-selective, and the enzyme reaction on this hydrophilic polymer of expectability can not be easy to be applied to hydrophobic polymer.
They the objective of the invention is to make polyolefin-wax modification so that can crosslinkedly keep hydrophobic performance simultaneously with polymerizable groups.
This purpose is formed (methyl) acrylated polyolefin-wax of component and is realized by comprising following copolymerization with polymerized form under formal every kind of situation:
A) at least a alkene that does not have other functional groups,
B1) at least a alkenyloxy alkyl (methyl) acrylate and/or allyloxy alkyl (methyl) acrylate
And/or
B2) at least a (methyl) acryloxyalkyl (methyl) acrylate and/or (methyl) acryloxyalkyl (methyl) acrylamide and
C) if suitable, at least aly be different from a), b1) and b2) and have a monomer of at least one functional group.
Here " in form " refer to relevant comonomer, especially have the monomer b1 of two polymerizable groups) and b2) need be in copolymerization use with specified form, but should think and mix in the multipolymer by abstract imagination.This is especially at monomer b1) and situation b2) under only refer to that in fact one of two polymerizable groups mix multipolymer and another polymerizable groups remains unchanged in polymkeric substance, at monomer b1) situation under, but (methyl) acrylate group of copolymerization remains unchanged.
Another object of the present invention provide a kind of can be with polyolefin-wax with polymerizable groups with the method for high conversion and highly selective modification.Synthetic should under mild conditions, carrying out to obtain having low colour and highly purified product.In addition, should save use activation (methyl) acrylic acid derivative such as monoxime or (methyl) vinyl acrylate.
To cause crosslinkedly with compound as the obviously simple method of comonomer, and therefore cause the big raising of molar mass with two polymerizable groups.
This purpose realizes with (methyl) acroleic acid esterification or with method that the transesterify of (methyl) acrylate prepares (methyl) acrylated polyolefin-wax by a kind of polyolefin-wax of having hydroxyalkyl of making.
The inventive method makes and can use simple starting raw material under mild conditions with good chemical and space time yield that i.e. (methyl) vinylformic acid and (methyl) acrylate preparation has good colour (methyl) acrylated polyolefin-wax.
Do not need to use activatory (methyl) acrylic acid derivative as (methyl) vinyl acrylate.
In this article, statement (methyl) vinylformic acid nail base vinylformic acid and vinylformic acid, preferred vinylformic acid.
Monomer a) is at least a alkene that does not have other functional groups, the preferred alkene that only has two keys, preferred especially alpha-olefin, very particularly preferably ethene.
Olefin) preferably do not have other heteroatomic pure hydrocarbon.
The example of alkene is ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 1-hexene, 1-octene, number-average molecular weight M nBe the daltonian polyisobutene of 100-1000, cyclopentenes, tetrahydrobenzene, divinyl, isoprene and vinylbenzene.
The example of alpha-olefin is the alkene of formula (I):
R 1-CH＝CH 2
R wherein 1Maybe can choose the C of the one or more oxygen in interval and/or sulphur atom and/or one or more replacement or unsubstituted imino-wantonly for hydrogen 1-C 18Alkyl, preferred hydrogen or C 1-C 4Alkyl, preferred especially hydrogen.
Preferred alpha-olefin is ethene, propylene, 1-butylene, iso-butylene, 1-amylene, 1-hexene and 1-octene, optimal ethylene, propylene, iso-butylene, special optimal ethylene or propylene, very particularly preferably ethene.
Monomer b1) is at least a alkenyloxy alkyl (methyl) acrylate and/or allyloxy alkyl (methyl) acrylate, preferred at least a alkenyloxy alkyl (methyl) acrylate.
These for example are the compound of formula (II):
Figure A20068000670700091
Wherein
R 2And R 4Be hydrogen or methyl separately independently of each other,
R 3For optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 2-C 20Alkylidene group, C 5-C 12Cycloalkylidene or C 6-C 12Arylidene or at interval one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-and/or one or more cycloalkyl ,-(CO)-,-O (CO) O-,-(NH) (CO) O-,-O (CO) (NH)-,-O (CO)-or-(CO) C of O- 2-C 20Alkylidene group.
Monomer b2) is at least a (methyl) acryloxyalkyl (methyl) acrylate and/or (methyl) acryloxyalkyl (methyl) acrylamide.Preferred (methyl) acryloxyalkyl (methyl) acrylate.
The example of (methyl) acryloxyalkyl (methyl) acrylate is the compound of formula (III):
Figure A20068000670700101
The example of (methyl) acryloxyalkyl (methyl) acrylamide is the compound of formula (IIIa):
Figure A20068000670700102
Wherein
R 5And R 7Be hydrogen or methyl separately independently of each other, and
R 6For optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 1-C 20Alkylidene group, C 5-C 12Cycloalkylidene or C 6-C 12Arylidene or at interval one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-and/or one or more cycloalkyl ,-(CO)-,-O (CO) O-,-(NH) (CO) O-,-O (CO) (NH)-,-O (CO)-or-(CO) C of O- 2-C 20Alkylidene group.
If suitable, monomer c) at least aly be different from a), b1) and b2) and have a monomer of at least one functional group.
In these monomers, functional group is the atomic radical that comprises the atom outside de-carbon or the hydrogen.Example is hydroxyl, replacement, the single replacement or dibasic amino, sulfydryl, ether, carboxyl, carboxylic acid anhydride, sulfonic acid, phosphoric acid, phosphonic acids, carboxylic acid amides, carboxylicesters, carboxylic acid anhydride, sulphonate, phosphoric acid ester, phosphonic acid ester or nitrile group.Preferred hydroxyl, amino, ether, carboxyl and carboxylate group, preferred especially ether, carboxyl and carboxylate group.
As monomer c), can for example mention (methyl) vinylformic acid C 1-C 20Alkyl ester comprises the vinyl acetate of the carboxylic acid of 20 carbon atoms at the most, and olefinically unsaturated nitriles comprises the vinyl ether of the alcohol of 1-10 carbon atom, and α, beta-unsaturated carboxylic acid and acid anhydride thereof.
As (methyl) alkyl acrylate, preferably has C 1-C 10Those of alkyl, preferable methyl methyl acrylate, methyl acrylate, n-butyl acrylate, ethyl propenoate and 2-EHA.
Especially the mixture of (methyl) alkyl acrylate also is fit to.
The preferred vinyl laurate of vinyl acetate, stearic acid vinyl ester, propionate and vinyl-acetic ester with carboxylic acid of 1-20 carbon atom.
α, beta-unsaturated carboxylic acid and acid anhydride thereof can for example be vinylformic acid, methacrylic acid, fumaric acid, Ba Dousuan, methylene-succinic acid, toxilic acid or maleic anhydride, preferred vinylformic acid.
The example of nitrile is vinyl cyanide and methacrylonitrile.
The Vinyl Ether that is fit to for example is vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl Octyl Ether.
Also can use N-vinyl formamide, N-vinyl pyrrolidone and N-caprolactam.
In above-mentioned definition,
Optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 2-C 20Alkylidene group for example is 1,1-ethylidene, ethylene, 1,1-propylidene, propylene, trimethylene, 1,1-butylidene, 1,2-butylidene, 1,3-butylidene, 1,4-butylidene, hexamethylene, 2-methyl isophthalic acid, 3-propylidene, 2-ethyl-1,3-propylidene, 2,2-dimethyl-trimethylene, 2,2-dimethyl-tetramethylene
Optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 1-C 20Alkylidene group additionally comprises methylene radical,
Optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 5-C 12Cycloalkylidene for example is cyclopropylidene, cyclopentylidene, cyclohexylidene, inferior ring octyl group, inferior cyclo-dodecyl,
Optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the one or more oxygen in interval of heterocyclic substituted and/or sulphur atom and/or one or more replacement or unsubstituted imino-and/or one or more cycloalkyl ,-(CO)-,-O (CO) O-,-(NH) (CO) O-,-O (CO) (NH)-,-O (CO)-or-(CO) C of O- 2-C 20Alkylidene group for example is 3-oxa--pentamethylene, 3,6-two oxa-s-1,8-is octylene, 3,6,9-trioxa-1, the inferior undecyl of 11-, 4-oxa--1, the inferior heptyl, 4 of 7-, 8-two oxa-s-1, the inferior undecyl, 4,8 of 11-, 12-trioxa-1, the inferior pentadecyl of 15-, 5-oxa--nonamethylene, 5,10-two oxa-s-1, the inferior tetradecyl of 14-, 3-oxa--2,5-dimethyl-pentamethylene, 3,6-two oxa-s-2,5,8-trimethylammonium-1,8-is octylene, 3-oxa--1,4-dimethyl-pentamethylene and 3,6-two oxa-s-1,4,7-trimethylammonium-1,8-is octylene
Optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 6-C 12Arylidene for example is 1,2-, 1, and 3-or 1, the 4-phenylene, 4,4 '-diphenylene, Ben Yajiaji or xylylene, and
Can choose the C of the one or more oxygen in interval and/or sulphur atom and/or one or more replacement or unsubstituted amino wantonly 1-C 18Alkyl or C 2-C 18Alkyl for example is a methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, the 2-ethylhexyl, 2,4, the 4-tri-methyl-amyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, the 1-dimethyl propyl, 1, the 1-dimethylbutyl, 1,1,3, the 3-tetramethyl butyl, benzyl, the 1-phenylethyl, the 2-phenylethyl, α, α-Er Jiajibianji, diphenyl-methyl, the p-methylphenyl methyl, 1-(to butyl phenyl) ethyl, p-chlorobenzyl, 2, the 4-dichloro benzyl, to methoxy-benzyl, the m-oxethyl benzyl, the 2-cyano ethyl, 2-cyano group propyl group, 2-methoxycarbonyl ethyl, 2-ethoxy carbonyl ethyl, 2-butoxy carbonyl propyl group, 1,2-two (methoxycarbonyl) ethyl, the 2-methoxy ethyl, the 2-ethoxyethyl group, the 2-butoxyethyl group, diethoxymethyl, the diethoxy ethyl, 1,3-dioxolane-2-base, 1,3-two  alkane-2-base, the 2-methyl isophthalic acid, 3-dioxolane-2-base, the 4-methyl isophthalic acid, 3-dioxolane-2-base, 2-isopropoxy ethyl, 2-butoxy propyl group, 2-octyloxy ethyl, chloromethyl, the 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl, 2-methoxyl group sec.-propyl, the 2-ethoxyethyl group, the butyl thiomethyl, 2-dodecyl sulphur ethyl, 2-phenyl sulphur ethyl, 2,2, the 2-trifluoroethyl, 2-phenoxy group ethyl, the 2-phenoxy propyl, the 3-phenoxy propyl, 4-phenoxy group butyl, 6-phenoxy group hexyl, the 2-methoxy ethyl, the 2-methoxy-propyl, the 3-methoxy-propyl, 4-methoxyl group butyl, 6-methoxyl group hexyl, the 2-ethoxyethyl group, the 2-ethoxycarbonyl propyl, the 3-ethoxycarbonyl propyl, 4-oxyethyl group butyl or 6-oxyethyl group hexyl, preferable methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, the 2-ethylhexyl, 2,4, the 4-tri-methyl-amyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1, the 1-dimethyl propyl, 1, the 1-dimethylbutyl, 1,1,3, the 3-tetramethyl butyl, benzyl, the 1-phenylethyl, the 2-phenylethyl, α, α-Er Jiajibianji, diphenyl-methyl, the p-methylphenyl methyl, 1-(to butyl phenyl) ethyl, p-chlorobenzyl, 2, the 4-dichloro benzyl, the 2-cyano ethyl, 2-cyano group propyl group, chloromethyl, the 2-chloroethyl, trichloromethyl, trifluoromethyl, 1,1-dimethyl-2-chloroethyl and 2,2, the 2-trifluoroethyl.
R 1Example be hydrogen, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, n-hexyl, n-octyl, positive decyl and dodecyl.
Preferred hydrogen, methyl, ethyl, n-propyl, normal-butyl, n-pentyl and n-hexyl, special preferable methyl, ethyl, normal-butyl and n-hexyl, very particularly preferably methyl.
R 2Example be hydrogen and methyl, preferred hydrogen.
R 3Example be ethylene, propylene, 1, the 3-propylidene, 1, the 2-butylidene, 1, the 3-butylidene, 1, the 4-butylidene, hexamethylene, octamethylene, 1, the inferior decyl of 10-, 1, the inferior dodecyl of 12-, the 2-methyl isophthalic acid, the 3-propylidene, 2-ethyl-1, the 3-propylidene, 2,2-dimethyl-trimethylene, 2,2-dimethyl-tetramethylene, 3-oxa--pentamethylene, 3,6-two oxa-s-octamethylene, 3,6,9-trioxa-1, the inferior undecyl of 11-, 4-oxa--1, the inferior heptyl of 7-, 4,8-two oxa-s-1, the inferior undecyl of 11-, 4,8,12-trioxa-1, the inferior pentadecyl of 15-, 5-oxa--nonamethylene, 5,10-two oxa-s-1, the inferior tetradecyl of 14-, 3-oxa--2,5-dimethyl-pentamethylene, 3,6-two oxa-s-2,5,8-trimethylammonium-octamethylene, 3-oxa--1,4-dimethyl-1,5-pentylidene and 3,6-two oxa-s-1,4,7-trimethylammonium-1,8-is octylene, 1,2-or 1, the 3-cyclopentylidene, 1,2-, 1,3-or 1, the 4-cyclohexylidene, inferior ring octyl group or inferior cyclo-dodecyl.
R 4Example be hydrogen and methyl, preferred hydrogen.
R 5Example be hydrogen and methyl, preferred hydrogen.
R 6Example be methylene radical, ethylene, propylene, 1, the 3-propylidene, 1, the 2-butylidene, 1, the 3-butylidene, 1, the 4-butylidene, hexamethylene, octamethylene, 1, the inferior decyl of 10-, 1, the inferior dodecyl of 12-, the 2-methyl isophthalic acid, the 3-propylidene, 2-ethyl-1, the 3-propylidene, 2,2-dimethyl-trimethylene, 2,2-dimethyl-tetramethylene, 3-oxa--pentamethylene, 3,6-two oxa-s-octamethylene, 3,6,9-trioxa-1, the inferior undecyl of 11-, 4-oxa--1, the inferior heptyl of 7-, 4,8-two oxa-s-1, the inferior undecyl of 11-, 4,8,12-trioxa-1, the inferior pentadecyl of 15-, 5-oxa--nonamethylene, 5,10-two oxa-s-1, the inferior tetradecyl of 14-, 3-oxa--2,5-dimethyl-pentamethylene, 3,6-two oxa-s-2,5,8-trimethylammonium-octamethylene, 3-oxa--1,4-dimethyl-1,5-pentylidene and 3,6-two oxa-s-1,4,7-trimethylammonium-1,8-is octylene, 1,2-or 1, the 3-cyclopentylidene, 1,2-, 1,3-or 1, the 4-cyclohexylidene, inferior ring octyl group or inferior dodecyl.
R 7Example be hydrogen and methyl, preferred hydrogen.
Preferred monomer b1) be 2-vinyl oxygen base ethyl (methyl) acrylate, 4-vinyl oxygen Ji Dingji (methyl) acrylate, 6-vinyl oxygen base hexyl (methyl) acrylate, 2 (allyl group oxygen base) ethyl (methyl) acrylate, polyoxyethylene glycol mono allyl ether list (methyl) acrylate, preferred especially 4-vinyl oxygen Ji Dingji (methyl) acrylate.
Preferred monomer b2) be 2-(methyl) acryl ethyl (methyl) acrylate; 4-(methyl) acryl butyl (methyl) acrylate; 6-(methyl) acryl hexyl (methyl) acrylate; 8-(methyl) acryl octyl group (methyl) acrylate; 10-(methyl) acryl decyl (methyl) acrylate; 12-(methyl) acryl dodecyl (methyl) acrylate; 2-(methyl) acryl propyl group (methyl) acrylate; polypropylene glycol two (methyl) acrylate; polyoxyethylene glycol two (methyl) acrylate; N-(methyl) acryl methyl (methyl) acrylamide.
The present invention contains b1) polyolefin-wax have following composition (with mole %) usually:
A) 75-99.9 mole %, preferred 80-99.5 mole %, preferred especially 85-99 mole %,
B1) 0.1-15 mole %, preferred 0.5-15 mole %, preferred especially 1-15 mole %,
C) 0-25 mole %, preferred 0-15 mole %, preferred especially 0-10 mole %, very particularly preferably 0-5 mole %, especially 0 mole of %,
Condition is and is 100 moles of %.
The present invention contains b2) polyolefin-wax have following composition (with mole %) usually:
A) 75-99.9 mole %, preferred 80-99.5 mole %, preferred especially 85-99 mole %,
B2) 0.1-25 mole %, preferred 0.5-20 mole %, preferred especially 1-15 mole %,
C) 0-25 mole %, preferred 0-15 mole %, preferred especially 0-10 mole %, very particularly preferably 0-5 mole %, especially 0 mole of %,
Condition is and is 100 moles of %.
Polyolefin-wax of the present invention also can comprise the b1 of above-mentioned amount) and b2) two kinds.
The number-average molecular weight M of polyolefin-wax of the present invention nBe 20000g/mol at the most, preferred 18000g/mol at the most, especially preferably 15000g/mol at the most.
The present invention further provides a kind of method for preparing polyolefin-wax of the present invention.
This method comprises the steps:
(1) prepare polyolefin-wax by following monomer copolymerization:
A) at least a alkene that does not have other functional groups,
B1) at least a hydroxyalkyl alkenyl ether and/or hydroxyalkyl allyl ethers and/or
B2) at least a hydroxyalkyl (methyl) acrylate and/or hydroxyalkyl (methyl) acrylamide and
C) if suitable, at least a A of being different from), B1) and B2) and have a monomer of at least one functional group,
(2) if suitable, the polyolefin-wax that obtains is purified,
(3) polyolefin-wax that will obtain by (1) or (2) with (methyl) acroleic acid esterification and/or with the transesterify of (methyl) acrylate,
(4) if suitable, (methyl) acrylated polyolefin-wax that obtains is purified.
Monomer A) can be a) identical with above-mentioned monomer.
Monomer C) can with above-mentioned monomer c) identical.
Monomers B 1) is at least a hydroxyalkyl alkenyl ether or hydroxyalkyl allyl ethers, preferred at least a hydroxyalkyl alkenyl ether.
These for example are the ether of formula (IV):
Figure A20068000670700151
R wherein 2And R 3Definition as above.
Comonomer B1) example is 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyl hexyl vinyl ether, ethylene glycol monoallyl ether, polyoxyethylene glycol mono allyl ether, 4-hydroxybutyl allyl ethers, 6-hydroxyl hexyl allyl ethers, Diethylene Glycol mono allyl ether, propylene glycol mono allyl ether, dipropylene glycol mono allyl ether, 1, ammediol mono allyl ether, glycerol mono allyl ether and TriMethylolPropane(TMP) mono allyl ether.
Preferred 4-hydroxybutyl vinyl ether.
Monomers B 2) is at least a hydroxyalkyl (methyl) acrylate or hydroxyalkyl (methyl) acrylamide, preferred at least a hydroxyalkyl (methyl) acrylate.
Example is the compound of formula V:
Figure A20068000670700161
R wherein 5And R 6Definition as above.
Comonomer B2) example is 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 2-hydroxyl fourth-1-base (methyl) acrylate, 4-hydroxyl fourth-1-base (methyl) acrylate, 3-hydroxyl fourth-1-base (methyl) acrylate, the 6-hydroxyl oneself-1-base (methyl) acrylate, 8-hydroxyl suffering-1-base (methyl) acrylate, 3-hydroxyl-2,2-dimethyl propyl (methyl) acrylate, 2-ethyl-3-hydroxyl oneself-1-base (methyl) acrylate, 2,4-diethyl-5-hydroxyl-Xin-1-base (methyl) acrylate, TriMethylolPropane(TMP) list (methyl) acrylate, single (methyl) acrylate of tetramethylolmethane list (methyl) acrylate or glycerol, polypropylene glycol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, N-methylol methacrylamide (=N-(hydroxymethyl) Methacrylamide) and N-(hydroxymethyl) Methacrylamide.
Preferred comonomer B2 be 2-hydroxyethyl (methyl) acrylate, 2-hydroxypropyl (methyl) acrylate, 3-hydroxypropyl (methyl) acrylate, 4-hydroxyl fourth-1-base (methyl) acrylate and 6-hydroxyl oneself-1-base (methyl) acrylate, preferred especially 2-hydroxyethyl (methyl) acrylate and 2-hydroxypropyl (methyl) acrylate.
Contain B1) the composition following usually (with mole %) of polyolefin-wax:
A) 75-99.9 mole %, preferred 80-99.5 mole %, preferred especially 85-99 mole %,
B1) 0.1-15 mole %, preferred 0.5-15 mole %, preferred especially 1-15 mole %,
C) 0-25 mole %, preferred 0-15 mole %, preferred especially 0-10 mole %, very particularly preferably 0-5 mole %, especially 0 mole of %,
Condition is and is 100 moles of %.
Contain B2) the composition following usually (with mole %) of polyolefin-wax:
A) 75-99.9 mole %, preferred 80-99.5 mole %, preferred especially 85-99 mole %,
B2) 0.1-25 mole %, preferred 0.5-20 mole %, preferred especially 1-15 mole %,
C) 0-25 mole %, preferred 0-15 mole %, preferred especially 0-10 mole %, very particularly preferably 0-5 mole %, especially 0 mole of %,
Condition is and is 100 moles of %.
Also can use the B1 of above-mentioned amount in the methods of the invention) and B2) two kinds.
The preparation of polyolefin-wax is as follows usually:
Preparing polyolefin-wax of the present invention by the inventive method can carry out in agitated autoclave or high pressure tubular reactors.Preferably in agitated autoclave, prepare.The agitated autoclave itself that is used for the inventive method is known, it describes visible Ullmann ' s Encyclopedia of Industrial Chemistry, the 5th edition, keyword: Waxes, the A28 volume, the 146th page reaches each page subsequently, Verlag ChemieWeinheim, Basle, Cambridge, New York, Tokyo, 1996.
Their length: the diameter ratio is mainly 5: 1-30: 1, preferred 10: 1-20: 1.Same spendable high pressure tubular reactors is described in Ullmann ' s Encyclopedia of IndustrialChemistry equally, the 5th edition, keyword: Waxes, the A28 volume, the 146th page reaches each page subsequently, Verlag Chemie Weinheim, Basle, Cambridge, New York, Tokyo is in 1996.
Being suitable for the polymeric pressure condition is the 500-4000 crust, preferred 1500-2500 crust.Temperature of reaction is 170-300 ℃, preferred 200-280 ℃.
The inventive method can be carried out in the presence of conditioning agent.Used conditioning agent for example is hydrogen or aliphatic aldehyde or aliphatic ketone.
Example is formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, valeraldehyde, isovaleric aldehyde, acetone, ethyl methyl ketone, diethyl ketone, isobutyl methyl ketone, pimelinketone, cyclopentanone and cyclododecanone.
Very particularly preferably propionic aldehyde or ethyl methyl ketone are as conditioning agent.
Other fit closely conditioning agents are Alkylaromatics, for example the isomer of toluene, ethylbenzene or one or more dimethylbenzene.
Other fit closely conditioning agents are unbranched aliphatic hydrocrbon such as propane.Good especially conditioning agent is branched aliphatic hydrocarbon such as Trimethylmethane, iso-pentane, octane-iso or the Permethyl 99A. (2,2,4,6, the 6-five methylheptane) with uncle H atom.Permethyl 99A. is for very particularly suitable.
The amount of used conditioning agent is corresponding to the convention amount that is used for high pressure polymerization process.
As the initiator that is used for radical polymerization, can use conventional free radical initiator such as organic superoxide, oxygen or azo-compound.The mixture of multiple radical initiator also is fit to.
As radical initiator, use one or more to be selected from the superoxide of following commercially available material: the didecyl acyl peroxide, 2,5-dimethyl-2,5-two (2-ethyl hexanoyl base peroxide) hexane, tert-pentyl peroxide-2-ethylhexanoate, tert-pentyl peroxide pivalate, the biphenyl acyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy diethylacetic acid ester, t-butyl peroxy diethyl isobutyrate, as 1 of isomer mixture, 4-two (t-butyl peroxy carbonyl) hexanaphthene, the tertiary butyl is crossed different pelargonate 1,1-two (t-butyl peroxy)-3,3, the 5-trimethyl-cyclohexane, 1,1-two (t-butyl peroxy) hexanaphthene, the methyl-isobutyl ketone peroxide, BPIC (t butyl peroxy isopropyl carbonate), 2,2-two-tertiary butyl-peroxide butane or t-butyl peroxy acetic ester; T-butyl peroxy benzoic ether, two t-amyl peroxy things, diisopropylbenzyl superoxide, isomery two (t-butyl peroxy sec.-propyl) benzene, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane, tert butyl isopropyl benzene peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) oneself-3-alkynes, ditertiary butyl peroxide, 1,3-di-isopropyl list hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide; Or dimerization or trimeric ketone peroxide.
Their method of dimerization or trimeric ketone peroxide and preparation is known by EP-A 0813550.
Particularly suitable superoxide is ditertiary butyl peroxide, t-butyl peroxy pivalate, tert-pentyl peroxide pivalate, the different pelargonate of t-butyl peroxy and dibenzoyl superoxide and their mixture.The azo-compound that can mention for example is Diisopropyl azodicarboxylate (" AIBN ").Radical initiator is introduced to be used for the polymeric convention amount.
The inventive method is preferably carried out in the presence of solvent, with regard to the object of the invention, with small proportion be present in the inventive method and for example be used for the stabilized radical initiator or the mineral oil of initiator counting and other solvents as the solvent of the inventive method.Other solvents for example are aromatic solvent.Particularly preferred aromatic hydrocarbon is toluene, xylene isomer and ethylbenzene.
Aromatic hydrocarbons, (ring) aliphatic hydrocrbon, alkyl chain alkanoic acid ester, alkoxylated alkyl alkanoates and composition thereof.
Preferred especially monoalkylation or many alkylated benzenes and naphthalene, alkyl chain alkanoic acid ester and alkoxylated alkyl alkanoates and composition thereof.
As the aromatic hydrocarbon mixture, preferably mainly comprise aromatics C 7-C 14Hydrocarbon and can to comprise boiling point be those of 110-300 ℃; Preferred especially toluene, o-Xylol, m-xylene or p-Xylol, Three methyl Benzene isomer, tetramethyl-benzene isomer, ethylbenzene, isopropyl benzene, tetraline and comprise the mixture of this class hydrocarbon.
Example is the Solvesso from ExxonMobil Chemical The trade mark, especially Solvesso 100 (CAS No.64742-95-6 mainly is C 9And C 10Aromatic hydrocarbon, boiling point is for about 154-178 ℃), 150 (the about 182-207 of boiling point ℃) and 200 (CAS No.64742-94-5) and from the Shellsol of Shell The trade mark.The hydrocarbon mixture of alkane, naphthenic hydrocarbon and aromatic hydrocarbon also is at commercially available under one's name (the Kristall  l 30 for example of Kristall  l, the about 158-198 of boiling point ℃ or Kristall  l 60:CASNo.64742-82-1), petroleum solvent (equally for example CAS No.64742-82-1) or solvent naphtha (light: the about 155-180 of boiling point ℃, heavy: the about 225-300 of boiling point ℃).The aromatic content of this hydrocarbon mixture is preferably greater than 95 weight % usually greater than 90 weight %, is preferably greater than 98 weight % especially, very particularly preferably greater than 99 weight %.Can advantageously use the hydrocarbon mixture of low especially naphthalene content.
Usually monomer is introduced together or respectively.The ratio that is metered into is not usually just in time corresponding to the unitary ratio of the monomer structure in the polyolefin-wax of the present invention, this is because hydroxyalkyl alkenyl ether and hydroxyalkyl (methyl) acrylate B1) and B2) mix in the polyolefin-wax of the present invention usually than alkene, especially ethene is easier and faster.
Polyolefin-wax of the present invention can fabulously disperse; Especially they can be particularly well with molten state emulsification.Therefore the present invention provides the dispersion that comprises polyolefin-wax of the present invention, especially water dispersion.
The purification (2) of the polyolefin-wax that obtains like this from step (1) is for optional, can be by with solvent wash wax and subsequently with their filtrations or centrifugally go out to carry out if suitable.
For removing unreacted monomer, vacuum distilling or stripping operation also are favourable.For example the monomer that will mainly measure is isolated by distillation in a first step, subsequently residual monomer is inert gasses by being used under the reaction conditions, preferred oxygen-containing gas, preferred especially air or air/nitrogen mixture, or remove with carbonic acid gas or steam stripping.
Usually do not need to purify, preferably do not purify.
If carry out step (3), then use following program usually with the form of esterification:
Esterification equipment comprises reactor with circulating evaporator and the stacked distillation tower with condenser and phase separation container.
Reactor can be for example for having the reactor of double-walled heating and/or internal heating coil pipe.The preferred reactor that uses with external heat exchanger and natural convection or pump circulation (use pump), the natural convection that special preferred cycle materials flow does not produce by machinery.
The cycle gasification device that is fit to is well known by persons skilled in the art and for example is described in R.Billet, Verdampfertechnik, and HTB-Verlag, Bibliographisches Institut Mannheim is in 1965,53.The example of circulating evaporator is tube and shell heat exchanger, plate-type heat exchanger etc.
Certainly, also can be present in the circulation by a plurality of interchanger.
Distillation tower is for known type own and have conventional internals.As the tower internals, can use all conventional internals in principle, for example column plate, regular packing and/or random filler.In column plate, preferred bubble cap plate, sieve plate, valve tray, Thorman tray (Thormann trays) and/or double pass tray; In the regular packing type, preferably comprise those of ring, volution, saddle packing body or braiding.
5-20 theoretical tray is generally enough.
Condenser and separation vessel are general type.
(methyl) vinylformic acid uses with the hydroxyl equivalent amount based on polyolefin-wax usually with the polyolefin-wax that has hydroxyalkyl, but also can use substoichiometric amount or excessive (methyl) vinylformic acid.
Preferably with (methyl) acrylic acid excessive hydroxyl (equivalent) 5-100 mole % that whenever treats esterification that is set at, preferred 5-50 mole %, preferred especially 5-25 mole %, especially 5-10 mole %.
As esterifying catalyst, can use conventional mineral acid and sulfonic acid, preferably sulfuric acid, phosphoric acid, alkylsulphonic acid (for example methanesulfonic, trifluoromethayl sulfonic acid) and aryl sulfonic acid (for example Phenylsulfonic acid, tosic acid or Witco 1298 Soft Acid) or its mixture, but the acid ion exchanger also is fine.
Special preferably sulfuric acid, methylsulfonic acid and tosic acid or its mixture.
They are usually with based on esterification mixture, 0.1-5 weight %, and preferred 0.5-5 weight %, preferred especially 1-4 weight %, very particularly preferably the amount of 2-4 weight % is used.
If necessary, esterifying catalyst can be removed from reaction mixture by ion-exchanger.In this case, ion-exchanger directly can be introduced in the reaction mixture subsequent filtration or make reaction mixture pass through the ion-exchanger bed.
Preferably esterifying catalyst is stayed in the reaction mixture and and removed (face as follows) by washing.
The stopper that is fit to that can be used for esterification is a thiodiphenylamine, if suitable monohydric phenol or polyphenol with one or more alkyl, for example alkylphenol such as neighbour, between or p-cresol (cresols), the 2-tertiary butyl-4-cresols, the 6-tertiary butyl-2, the 4-xylenol, 2,6-two-tertiary butyl-4-cresols, the 2-toluhydroquinone, 2,5-two-tertiary butylated hydroquinone, the 2-tert-butyl phenol, the 4-tert-butyl phenol, 2,4-two-tert-butyl phenol, 2-methyl-4-tert-butyl phenol, the 4-tertiary butyl-2, the 6-xylenol, 2,5-two-tertiary butylated hydroquinone, toluene hydroquinone or 2,2 '-methylene-bis (the 6-tertiary butyl-4-cresols), hydroxyl phenol such as quinhydrones, catechol (1, the 2-dihydroxy-benzene) or benzoquinones, amino-phenol such as p-aminophenol, nitrosophenol such as p-Nitrosophenol, alkoxy phenol such as 2-first-oxygen base phenol (methyl catechol, the pyrocatechol monomethyl ether), 2-oxyethyl group phenol, different third-oxygen the base of 2-phenol, 4-methoxyl group phenol (Hydroquinone monomethylether), one or two-tertiary butyl-4-methoxyl group phenol, tocopherol such as alpha-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxyl benzofuran (2,2-dimethyl-7-hydroxyl Dihydrobenzofuranes), phosphide such as triphenyl phosphite, the alkyl ester of Hypophosporous Acid, 50 or phosphorous acid, copper or manganese salt, cerium salt, nickel salt, chromic salts or mantoquita such as muriate, vitriol, salicylate, tosylate, acrylate or acetate, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base, 4-oxo-2,2,6,6-tetramethyl piperidine-N-oxygen base, 4-acetoxyl group-2,2,6, the 6-tetramethyl piperidine, 2,2,6, the 6-tetramethyl piperidine, 4,4 ', 4 " three (2,2,6; the 6-tetramethyl piperidine) phosphite or 3-oxo-2; 2,5,5-tetramethylpyrrolidi-e-N-oxygen base; N; N-pentanoic; N nitrosodiphenyl amine, N, N '-dialkyl group-Ursol D, thiodiphenylamine and composition thereof.
Preferred use is at least a from quinhydrones, Hydroquinone monomethylether, the 2-tertiary butyl-4-cresols, the 6-tertiary butyl-2,4-xylenol, 2,6-two-tertiary butyl-4-cresols, 2-tert-butyl phenol, 4-tert-butyl phenol, 2,4-two-tert-butyl phenol, 2-methyl-4-tert-butyl phenol, the 4-tertiary butyl-2, the compound of 6-xylenol, Hypophosporous Acid, 50, venus crystals, cupric chloride and Cupric salicylate is as stopper (mixture).
Stable for further helping, can there be oxygen-containing gas, the mixture (poor air) of preferred air or air and nitrogen.
Preferably this oxygen-containing gas is introduced the bottom section of tower and/or introduce circulating evaporator or pass through reaction mixture.
Stopper (mixture) is with based on esterification mixture, 0.01-1 weight %, and preferred 0.02-0.8 weight %, the total amount of preferred especially 0.05-0.5 weight % is used.
Be suitable for the solvent that azeotropic removes reaction water and especially be aliphatic series, cyclic aliphatic and aromatic hydrocarbon or its mixture.
Preferred Skellysolve A, normal hexane, normal heptane, hexanaphthene, methylcyclohexane, benzene, toluene or the dimethylbenzene of using.Preferred especially hexanaphthene, methylcyclohexane and toluene.
Consumption is based on pure and mild (methyl) vinylformic acid sum, 10-200 weight %, preferred 20-100 weight %, preferred especially 30-100 weight %.
Temperature of reaction is generally 60-140 ℃, and preferred 70-110 ℃, very particularly preferably 75-100 ℃.Initial temperature is usually less than 100 ℃, preferably less than 90 ℃, especially preferably less than 80 ℃.Outlet temperature in the esterification is generally than the high 5-30 of initial temperature ℃.Temperature in the esterification can be measured and adjust as described in DE-A 199 41 136 and DE-A 100 63 175 by the variation of solvent strength in the reaction mixture.
Esterification can also can or be lower than under the barometric point at superatmospheric pressure and carry out at barometric point; Preferably under barometric point, operate.
Reaction times is generally 3-20 hour, and preferred 5-15 hour, preferred 7-12 hour especially.
If reactions steps (3) is carried out with the form of transesterify, use following program usually:
Make lower (methyl) acrylate such as C 1-C 10Alkyl (methyl) acrylate, preferred C 1-C 4Alkyl (methyl) acrylate, special preferable methyl, ethyl or n-butyl, more preferred n-butyl and the polyolefin-wax that has hydroxyalkyl are with 1: 1-4: 1 ester: pure mol ratio is reacted in the presence of at least a catalyzer.
Transesterify can be in batches, semicontinuous or carry out continuously, preferably carry out in batches.
The inventive method can use the transesterification catalyst described in all prior aries to carry out, preferred titanium, manganese or aluminium-alcohol salt, and preferred especially titanium alkoxide especially is present in the titanium alkoxide of the alcohol in the transesterify.Other possible transesterification catalysts for example are the metallo-chelate of hafnium, titanium, zirconium or calcium, basic metal and magnesium alkoxide, organo-tin compound or calcium and lithium compound such as oxide compound, oxyhydroxide, carbonate or halogenide.
If under the pressure that reduces, isolate the alcohol that forms in the esterification is suitable by distillation or rectifying.If suitable, this can be by means of the nonreactive relatively gas stripping that is fit to.2-10 weight %) and comprise the alcohol that disengages less than 400ppm usually the representative of the residue that obtains is used for catalyst solution (the Ti content: of transesterify.Therefore, essentially no extra alcohol introduce in the ester interchange intermixture (in mixture＜100ppm).
When using titanate, the titanium content of reaction mixture is generally 0.01-1 weight %.
Transesterify one or more be connected in series and with the combined reactor of at least one stacked rectifying tower and condenser in carry out.
Temperature of reaction is generally 80-140 ℃, and preferred 100-130 ℃, pressure is generally 200 millibars to barometric point, preferred 300-800 millibar, preferred especially 400-600 millibar.
Under the situation of a plurality of reactors, the temperature in the different reactor can be identical or different, for example can raise or reduction along reactor.The preferred rising.
Heat can preferably provide by the outer loop vaporizer by wall heat and/or external heat exchanger or internal exchanger such as tubular type or plate-type heat exchanger.Rectifying tower be known type and have isolating active internals (for example bubble cap plate, Thorman tray, valve tray, sieve plate or double pass tray) or comprise random filler or regular packing.But condenser is similarly known type and off-line operation as tubular type or plate-type heat exchanger, or direct control is as quencher.The uniform mixing of reaction soln as being undertaken by stirring, pump circulation, pressure or natural circulation, is preferably undertaken by pressure or natural circulation in known manner.
According to the present invention, reaction zone of installing in device as distillation unit or the reactor and/or interchanger are used in and are inert gasses or gaseous mixture such as nitrogen, air, nitrogen/oxygen mixture, argon gas, helium, carbonic acid gas or carbon monoxide under the reaction conditions, preferred air or air/nitrogen mixture, especially oxygen level is 0.1-15 volume %, those of preferred 0.5-10 volume %, very particularly preferably oxygen level is that air/nitrogen mixture of 1-5 volume % washes continuously.Rinsing gas is preferably preferred in pressure that exists or natural-circulation evaporator to be passed through along the heat exchange surface that exists.
For this reason, rinsing gas is infeeded adjacent own the known suitable unrestrictedly feeder of heat exchange surface that passes and exist at pressure or under volume control, make rinsing gas materials flow and liquid countercurrent or and flow preferred Continuous Flow and cross heat exchange surface.
Rinsing gas can be preheated to the temperature of heat exchange medium, make the temperature of rinsing gas and the temperature of heat-transfer medium be more or less the same, preferably be not more than 10 ℃ in 15 ℃.
Under every kind of situation per hour based on the volume (=1 parts by volume) of the reaction mixture of post-reactor in the reactor neutralization reaction district, 0.1-100 parts by volume, preferred 0.2-80 parts by volume, preferred especially 0.5-70 parts by volume, especially 1-50 parts by volume rinsing gas are by interchanger or reaction zone.
Especially preferably make rinsing gas pass the interchanger that the reaction medium in reactor or the distillation tower heats therein.
The residence time in the reaction zone that comprises reactor and any post-reactor is 1-4 hour, preferred 1.5-3 hour.
The tower that is stacked on the reactor has 10-30 theoretical tray usually.Reflux ratio is generally 5-20: 1, and preferred 7-15: 1.
The lower alcohol that disengages in the transesterify is isolated at the top that is stacked in the rectifying tower on the reactor with part rudimentary (methyl) acrylate.
Distillation condition, for example the preferred selection of theoretical plate number and reflux ratio makes the zeotrope that rudimentary (methyl) acrylate content therein is higher than in the Azeotrope compositions of lower alkane pure and mild rudimentary (methyl) acrylate under condition separately take out at the top of tower.
The stabilization of tower can be passed through conventional stablizer or its mixture, for example above-mentioned those and carry out.
Stabilization can be in or be not under the existence of molecular oxygen carries out.Preferred thiodiphenylamine, quinhydrones, Hydroquinone monomethylether, 4-hydroxyl-2,2,6 of using, 6-tetramethyl piperidine-N-oxygen base, 4-oxo-2,2,6,6-tetramethyl piperidine-N-oxygen base, 2, the 6-tertiary butyl-p-cresol or its mixture are used for stabilization with the amount of 10-5000ppm in each case; Especially preferably use thiodiphenylamine or contain the thiodiphenylamine mixture, thiodiphenylamine/4-hydroxyl-2,2,6 especially, 6-tetramethyl piperidine-N-oxygen based mixtures is used for stabilization.Under every kind of situation, by starting raw material directly or by recirculation or reflux stream and add.
Stabilization is especially used and 100-1000ppm thiodiphenylamine and 10-500ppm4-hydroxyl-2,2,6, and 6-tetramethyl piperidine-N-oxygen base blended refluxes and carries out.
Stabilization preferably uses the mixture of this stablizer to carry out at the solution of rudimentary (methyl) acrylate.
Especially preferably the dissolved stabilizer blend is sprayed to condenser surface.
(methyl) that obtains like this by step (3) if the purification of acrylated polyolefin-wax for optional and suitable by use the aqueous solution, if suitable weakly alkaline solution unreacted (methyl) vinylformic acid of washing and subsequent filtration, centrifugal or separate phase and carry out.
Unreacted (methyl) vinylformic acid for removing or (methyl) acrylate, vacuum distilling or stripping operation also can be for favourable.For example, the monomer of mainly measuring is isolated by distillation in a first step, subsequently residual monomer is inert gasses, preferred oxygen-containing gas by being used under the reaction conditions, preferred especially air or air/nitrogen mixture, or with carbonic acid gas or steam stripping.
Usually, purification is useful and preferably carries out.
Yet what also be fit to can be for staying unreacted (methyl) vinylformic acid or (methyl) acrylate in the reaction mixture, and this is that these can play the effect (face as follows) of reactive thinner in polymerization subsequently owing to depend on the purposes of plan.
Temperature in distillation or the stripping operation is generally 80-160 ℃, and preferred 90-150 ℃, preferred 90-120 ℃ especially, corresponding pressure is generally the 20-500 millibar in the distillation, preferred 50-300 millibar, preferred especially 80-150 millibar.Stripping under atmospheric pressure carries out usually.
If it is suitable, still-process can by with above-mentioned under reaction conditions, be inert air-flow such as nitrogen or oxygen-containing gas such as air or air/nitrogen mixture substantially, especially oxygen level is 0.1-15 volume %, the mixture of preferred 0.5-10 volume %, very particularly preferably oxygen level is that air/nitrogen mixture of 1-5 volume % passes through reaction mixture.The passing through of rinsing gas of the present invention preferably combines with stripping process.
In particularly preferred embodiment of the present invention, esterification or transesterify in the reactions steps (3) are carried out in the presence of enzyme.
In reactions steps (3), with (methyl) acroleic acid esterification or preferably have the polyolefin-wax of hydroxyalkyl and at least a, preferably a kind of (methyl) acrylated thing (D) transesterify is carried out under the existence of the enzyme (E) of preferred a kind of catalytic esterification or transesterify at least a.
Compound (D) can be the ester of (methyl) vinylformic acid or (methyl) vinylformic acid and saturated alcohol, preferred (methyl) acrylic acid saturated C 1-C 10Alkyl ester or C 3-C 12Cycloalkyl ester, preferred especially (methyl) acrylic acid saturated C 1-C 4Alkyl ester.
With regard to this paper, the saturated finger of term does not have the compound (naturally except that the two keys of C=C in (methyl) acrylic acid units) of C-C Multiple Bonds.
The example of compound (D) is (methyl) vinylformic acid methyl, ethyl, normal-butyl, isobutyl-, n-octyl and 2-(ethyl hexyl) ester, 1,2-ethylene glycol bisthioglycolate (methyl) acrylate and single (methyl) acrylate, 1,4-butyleneglycol two (methyl) acrylate and single (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate and single (methyl) acrylate, trimethylolpropane tris (methyl) acrylate and tetramethylolmethane four (methyl) acrylate.
Preferred especially (methyl) vinylformic acid methyl, ethyl, normal-butyl and 2-(ethyl hexyl) ester, very particularly preferably (methyl) vinylformic acid methyl, ethyl and n-butyl.
If above-mentioned alcohol is optically active, then they preferably use with racemic form or as the mixture of diastereomer, also they can be used as pure enantiomorph or diastereomer or as the mixture of enantiomorph.
Enzyme urge esterification or with the transesterify of (methyl) acrylated thing usually at 0-100 ℃, preferred 20-80 ℃, preferred 20-70 ℃ especially, very particularly preferably carry out under 20-60 ℃.
The spendable enzyme of the present invention (E) for example is selected from lytic enzyme (E.C.3.-.-.-), wherein especially be selected from free form or chemistry or physical fixation esterase (E.C.3.1.-.-), lipase (E.C.3.1.1.3), glycosylase (E.C.3.2.-.-) and the proteolytic enzyme (E.C.3.4.-.-) on carrier, preferred fat enzyme, esterase or proteolytic enzyme, preferred especially esterase (E.C.3.1.-.-).Novozyme 435 (from the lipase of antarctic candida (Candida antarctica) B) or very particularly preferably from Alkaligenes (Alcaligenes sp.), Eurotium (Aspergillus sp.), mucor (Mucor sp.), Penicillium (Penicilium sp.), Geotrichum (Geotricum sp.), Rhizopus (Rhizopus sp.), Burkholder Pseudomonas (Burkholderiasp.), Candida (Candida sp.), pseudomonas (Pseudomonas sp.), thermophilic fungus belongs to the lipase of (Thermomyces sp.) or Pancreas Sus domestica, especially from antarctic candida B or from the lipase of Burkholder Pseudomonas.
The enzyme content of reaction medium is generally based on the used polyolefin-wax that has hydroxyalkyl, 0.1-10 weight %.
Reaction times is especially depended on the consumption of temperature, enzyme catalyst and active and desired transformation efficiency and the type that has the polyolefin-wax of hydroxyalkyl.The feasible conversion and at least 70% that is contained in the hydroxyl-functional in the polyolefin-wax that has hydroxyalkyl of the preferred selection in reaction times, preferably at least 80%, especially preferably at least 90%, very particularly preferably at least 95%, especially at least 97%, particularly at least 98% reaction.Thus, 1-72 hour usually, preferred 3-36 hour, preferred 3-24 hour was enough especially.
In alternate embodiment of the present invention, be contained in the polyolefin-wax that has hydroxyalkyl hydroxyl-functional only partial reaction to 10-80% for example, preferred 15-70%, preferred especially 20-60%, the degree of 25-55%, especially 30-50%, particularly 40-50% very particularly preferably.The polyolefin-wax of this partial esterification can be particularly advantageous for two sclerosis (face as follows) of solidifying.
In this case, form (methyl) acrylated polyolefin-wax that comprises the composition component of following copolymerization under formal every kind of situation with the form of copolymerization:
A) at least a alkene that does not have other functional groups,
B1) at least a alkenyloxy alkyl (methyl) acrylate and/or allyloxy alkyl (methyl) acrylate, and
B1) at least a hydroxyalkyl alkenyl ether and/or hydroxyalkyl allyl ethers,
And/or
B2) at least a (methyl) acryloxyalkyl (methyl) acrylate and/or (methyl) acryloxyalkyl (methyl) acrylamide and
B2) at least a hydroxyalkyl (methyl) acrylate and/or hydroxyalkyl (methyl) acrylamide and
B) if suitable, at least aly be different from a), b1) and b2) and have the monomer of at least one functional group, this is equally by the invention provides.
(methyl) acrylic compound (D) (based on (methyl) acrylic acid units) can be set in wide region with the mol ratio that has the polyolefin-wax (based on hydroxyl) of hydroxyalkyl, as 100: 1-1: 1, preferred 50: 1-1: 1, preferred especially 20: 1-1: 1, very particularly preferably 10: 1-1: 1.
Reaction can or not add solvent in organic solvent or its mixture and carry out.Preferably do not add solvent.Batch of material is anhydrous (promptly the water of Jia Ruing is less than 10 volume %, preferably less than 5 volume %, especially preferably less than 1 volume %, very particularly preferably less than 0.5 volume %) usually to a great extent.
The organic solvent that is fit to is for example for becoming known for the uncle's monohydroxy-alcohol such as the C of this purpose 3-C 6Alcohol, preferred tertiary butanols, tertiary amyl alcohol, pyridine, poly-C 1-C 4Aklylene glycol two C 1-C 4Alkyl oxide, preferred polyoxyethylene glycol two C 1-C 4Alkyl oxide is as 1,2-glycol dimethyl ether, diethylene glycol dimethyl ether, polyoxyethylene glycol dimethyl ether 500, methyl tertiary butyl ether, Ethyl Tertisry Butyl Ether, C 1-C 4Alkylene carbonate, especially Texacar PC, acetate C 3-C 6Alkyl ester, especially tert.-butyl acetate, THF, toluene, 1,3-dioxolane, acetone, isobutyl methyl ketone, ethyl methyl ketone, 1,4-two  alkane, t-butyl methyl ether, hexanaphthene, methylcyclohexane, toluene, hexane, Methylal(dimethoxymethane), 1,1-glycol dimethyl ether, acetonitrile and their single-phase or multiphase mixture.Can be advantageously be in close proximity to the two-phase of optimum temps of used enzyme or water or the alcohol that the three-phase zeotrope will disengage is isolated by boiling point.The alcohol of removing like this can be by being separated or the film steam separates and to remove.
Water-containing solvent can be added in the organic solvent if necessary, feasible depending on forms single-phase or heterogeneous reaction solution by organic solvent.The example of water-containing solvent is water and aqueous rare (for example 10-100mM) buffer reagent, for example pH for those of about 6-8 as potassiumphosphate or TRIS-HCl buffer reagent.
The water-content of reaction mixture is generally 0-10 volume %.Preferably not pre-treatment of reactant (dry, add water) and using.
Matrix is present in the reaction medium as solution, solid suspension or emulsion.The initial concentration of reactant is about 0.1-20mol/l, especially 0.15-10mol/l or 0.2-5mol/l.
Reaction can for example be carried out in tubular reactor or series connection stirred reactor continuously or in batches.
Reaction can be carried out in all are suitable for the reactor of this reaction.This reactor is well known by persons skilled in the art.Reaction is preferably carried out in stirred-tank reactor or fixed-bed reactor.
Can use the method for any hybrid reaction mixture.Do not need special whipping device.Reaction medium can be by one or more phase composites, if reactant can be suitable therein with molecular sieve dissolve, suspension or emulsification, and when the reaction beginning, mix, and if suitable one or many mixing in reaction process with zymin.Temperature is set at value required between the reaction period, and if suitable can the rising in reaction process or reduce.
Carry out if be reflected in the fixed-bed reactor, then fixed-bed reactor preferably are equipped with immobilized enzyme, then with the reaction mixture pumping by the tower of enzyme is housed.Also can react in fluidized-bed, in this case, enzyme uses with the form that is fixed on the carrier.Can be with the reaction mixture uninterrupted pumping by tower, the residence time and therefore required transformation efficiency can control by flow rate.Also can make reaction mixture cycle through tower, the alcohol that disengages can be distilled out under the pressure that reduces simultaneously by pump.
Remove under the situation of esterification anhydrate or situation in transesterify under remove the alcohol that discharges by alkyl (methyl) acrylate in a manner known way for example by the pressure, the azeotropic that reduce remove, absorption, pervaporation and by the film diffusion and carry out continuously or progressively.
This preferably realizes by distillation or by the semipolar linkage that is fit to by molecular sieve or zeolite (pore size for example is the 3-10 dust).
Yet, for the mixture of alkyl (methyl) acrylate that forms isolated azeotropic mixture often and female alcohol, also can directly reach the device that is used for preparing alkyl (methyl) acrylate with there with utilizing again in (methyl) acroleic acid esterification.
After reaction is finished, can further not purify or can in other steps, purify if necessary and the further reaction mixture that obtains by esterification or transesterify that uses.
Usually, purification step only comprises and used enzyme is isolated from reaction mixture and reaction product is isolated from any used organic solvent.
Enzyme separates by filtration, absorption, centrifugal or decant usually.Isolated enzyme can be used for other reaction subsequently.
Organic solvent is usually by distillation, rectifying or separate by filtration under the situation of solid reaction product.
For further purified reaction product, also can make it carry out chromatography.
Yet, preferably only used enzyme is separated in purification step with any used solvent.
It is gentle urging the reaction conditions in esterification or the transesterify at enzyme.Because low temperature and other mild conditionss avoid during reaction forming by product.Otherwise these may for example be derived from chemical catalyst or form by undesired used (methyl) acrylated thing radical polymerization, and it can only prevent by adding stablizer in addition.
In carrying out the present invention's reaction, except that the shelf-stable agent that is present in any case, can be with extra stablizer such as Hydroquinone monomethylether, thiodiphenylamine, phenol such as the 2-tertiary butyl-4-cresols, the 6-tertiary butyl-2,4-dimethyl phenol or N-oxygen base such as 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base, 4-oxo-2,2,6,6-tetramethyl piperidine-N-oxygen base for example adds in (methyl) acrylic compound (D) with the amount of 50-2000ppm.Esterification or transesterify are carried out under the existence of preferred air or air/nitrogen mixture advantageously at oxygen-containing gas.
Yet, urge in esterification or the transesterify at enzyme and can preferably save the adding stablizer.
In addition, enzyme catalyst can be removed from final product without a doubt.
If necessary, can be with reaction mixture for example by filtering, distillation, rectifying, chromatography, with ion-exchanger, sorbent treatment, neutral, acidity and/or alkaline washing, stripping or crystallization and purify.
The colour of (methyl) acrylated polyolefin-wax that the present invention obtains is generally below the 100APHA according to DIN ISO 6271, and is preferred below 80, preferred especially below 60, very particularly preferably below 40, especially below the 20APHA.
The polyolefin-wax that the present invention further provides polyolefin-wax of the present invention or like this preparation is as following purposes:
-be used for the dispersing of pigments agent,
-lubricant is particularly useful for the PVC polymkeric substance,
-be used for the matting agent of topcoating,
-be used for the tensio-active agent of printing-ink,
-leather coating,
-textile coating or
-radiation-hardenable and/or heat-setting coating composition.
The coating that comprises polyolefin-wax of the present invention has very high scuff resistance, hardness, chemical-resistant, comfortable sense of touch, elasticity and/or to the sticking power of hydrophilic base and hydrophobic substrates.
The present invention's available (methyl) acrylated polyolefin-wax can be advantageously used for monomer in poly-(methyl) acrylate or comonomer or as the reactive thinner in poly-(methyl) acrylate of thermal curable, radiation-hardenable and/or two curing.This poly-(methyl) acrylate for example is suitable for makes thermal curable, radiation-hardenable and/or double curing coating composition and at tackiness agent such as acrylic binder and the base-material in sealing agent.In addition, (methyl) acrylated polyolefin-wax can be used for urethane, for example in PU dispersion, PU foam, PU tackiness agent and the PU coating.The term thermal curable for example refers to can be additionally and a component and the two component topcoating systems of cross-linking reagent such as melamine resin or isocyanate derivates reaction.
Therefore the present invention relates to (methyl) acrylated polyolefin-wax by the inventive method preparation at radiation-hardenable or double curing coating composition, preferred finish paint, in the special preferably transparent varnish as the purposes of reactive thinner or base-material.Certainly, (methyl) of the inventive method preparation is if the acrylated polyolefin-wax also can be suitable be used as monomer in the polymerization with other polymerization single polymerization monomers as (methyl) methacrylic acid, (methyl) acrylate, vinylbenzene, divinyl, vinyl cyanide, vinyl-acetic ester, N-vinyl pyrrolidone, 4-hydroxy butyl vinyl ether or N-vinyl formamide.
Statement " two curing " means the coating composition thermal curable and can solidify by actinic radiation.For the present invention, actinic radiation is electromagnetic radiation such as visible light, UV radiation or X-radiation, especially UV radiation and granular radiation such as electron beam.
The radiation-hardenable base-material is can be by actinic radiation as defined above, especially by the UV radiation and solidified those.
The present invention further provides the topcoating preparaton that comprises (methyl) acrylated polyolefin-wax that can obtain by the inventive method.(methyl) acrylated polyolefin-wax can be used for priming paint or finish paint.Because their property, especially under the situation of branched p 0 lypropylene acid esters, for example the reduction of the scuff resistance of radiation curing Clear coating and elastic raising and viscosity is preferred in the finish paint.
Except that (methyl) acrylated polyolefin-wax, radiation-hardenable composition of the present invention can comprise following component in addition:
(G) but at least a polymerizable compound with a plurality of copolymerization ethylenically unsaturated groups,
(H) if suitable, reactive thinner,
(I) if suitable, light trigger and
(J) if suitable, the additive of other conventional topcoatings.
As compound (G), can use have a plurality of, but the i.e. compound of the radiation-hardenable of at least two copolymerization ethylenically unsaturated groups, free redical polymerization.
Compound (G) preferred vinyl ether or (methyl) acrylated compound, preferred especially acrylated compound under every kind of situation, promptly acrylic acid derivative.
Preferred vinyl ether or (methyl) acrylated compound (G) comprise 2-20, preferred 2-10, but 2-6 copolymerization ethylenical unsaturated double bonds very particularly preferably.
Preferred especially ethylenical unsaturated double bonds content is 0.1-0.7mol/100g, very particularly preferably the compound of 0.2-0.6mol/100g (G).
Except that other explanation, the number-average molecular weight M of compound (G) nPreferably less than 15000g/mol, preferred especially 300-12000g/mol, very particularly preferably 400-5000g/mol, especially 500-3000g/mol (using polystyrene to pass through gel permeation chromatography as eluent) as standard and tetrahydrofuran (THF).
(methyl) acrylated compound that can mention is (methyl) acrylate, and especially acrylate and polyfunctional alcohol, especially hydroxyl-removal do not comprise other functional groups outward or comprise the vinyl ether of the alcohol of ether group at the most.The example of this alcohol is a difunctional alcohol, ethylene glycol for example, the representative such as the Diethylene Glycol of propylene glycol and their higher condensation, triethylene glycol, dipropylene glycol, tripropylene glycol etc., 1,2-, 1,3-or 1,4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, the 3-methyl isophthalic acid, the 5-pentanediol, neopentyl glycol, alkoxylated phenols compound such as ethoxylation and/or propoxylation bis-phenol, 1,2-, 1,3-or 1,4 cyclohexane dimethanol, trifunctional or higher functional alcohol such as glycerol, TriMethylolPropane(TMP), trihydroxybutane, trimethylolethane, tetramethylolmethane, two TriMethylolPropane(TMP)s, Dipentaerythritol, Sorbitol Powder, mannitol and corresponding alkoxylate, especially ethoxylation and/or propylated alcohol.
Alkoxylated polymerization product can obtain by making the reaction of above-mentioned alcohol and oxyalkylene, especially ethylene oxide or propylene oxide in known manner.The preferred 0-10 of every hydroxy alkoxy base degree, promptly 1 mole of hydroxyl can be by 10 mole alkylene oxide alkoxylates at the most.
Other (methyl) acrylated compounds that can mention are polyester (methyl) acrylated thing, it is the vinyl ether of (methyl) acrylate or polyesterols, and carbamate (methyl) acrylate, epoxide (methyl) acrylate or trimeric cyanamide (methyl) acrylate.
Carbamate (methyl) acrylate for example can obtain if acrylate and suitable chain extension agent such as glycol, polyvalent alcohol, diamines, polyamines or two mercaptan or polythiol react by polyisocyanates and hydroxyalkyl (methyl).
The number-average molecular weight M of carbamate (methyl) acrylate nPreferred 500-20000g/mol, especially 750-10000g/mol, preferred especially 750-3000g/mol (using polystyrene to pass through gel permeation chromatography) as standard.
The content of carbamate (methyl) acrylate is preferably every 1000g carbamate (methyl) acrylate 1-5, preferred especially 2-4 mole (methyl) acrylic acid groups.
Epoxide (methyl) acrylate can obtain by epoxide and the reaction of (methyl) vinylformic acid.Possible epoxide for example is epoxidation of olefins or glycidyl ether, for example diglycidyl rthers of bisphenol-A or aliphatic glycidyl ether such as butanediol diglycidyl ether.
Trimeric cyanamide (methyl) acrylate can obtain by trimeric cyanamide and (methyl) vinylformic acid or the reaction of its ester.
The number-average molecular weight M of epoxide (methyl) acrylate and trimeric cyanamide (methyl) acrylate nPreferred 500-20000g/mol, preferred especially 750-10000g/mol, very particularly preferably 750-3000g/mol; Every 1000g epoxide (methyl) acrylate of the content of (methyl) acrylic acid groups or the preferred 1-5 of trimeric cyanamide (methyl) acrylate, preferred especially 2-4 (using polystyrene to pass through gel permeation chromatography as eluent) as standard and tetrahydrofuran (THF).
Other (methyl) acrylate that are fit to are for preferably on average comprising 1-5, especially 2-4, preferred especially 2 or 3 (methyl) acrylic acid groups, very particularly preferably carbonic ether (methyl) acrylate of 2 (methyl) acrylic acid groups.
The number-average molecular weight M of carbonic ether (methyl) acrylate nPreferably less than 3000g/mol, especially preferably less than 1500g/mol, especially preferably less than 800g/mol (use polystyrene as standard, solvent: tetrahydrofuran (THF) passes through gel permeation chromatography).
Carbonic ether (methyl) acrylate can be with plain mode by carboxylicesters and polynary, preferred dibasic alcohol (glycol such as hexylene glycol) transesterify and free subsequently OH obtain with (methyl) acroleic acid esterification or with (methyl) acrylate transesterify, for example as described in the EP-A 92269.They also can and polynaryly obtain as diol reaction by phosgene, urea derivatives.
As reactive thinner (compound (H)), but can use the radiation-hardenable that only has a unsaturated copolymerization group of olefinic, free redical or cationoid polymerisation compound.
Can for example mention C 1-C 20Alkyl (methyl) acrylate, has the vinyl aromatic compounds of 20 carbon atoms at the most, comprise the vinyl ester of the carboxylic acid of 20 carbon atoms at the most, olefinically unsaturated nitriles, the vinyl ether that comprises the alcohol of 1-10 carbon atom, α, beta-unsaturated carboxylic acid and acid anhydride thereof and have 2-8 carbon atom and the aliphatic hydrocrbon of 1 or 2 two key.
As (methyl) alkyl acrylate, preferably has C 1-C 10Those of alkyl, for example methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl propenoate and 2-EHA.
Especially the mixture of (methyl) alkyl acrylate also is fit to.
Vinyl ester with carboxylic acid of 1-20 carbon atom for example is vinyl laurate, stearic acid vinyl ester, propionate and vinyl-acetic ester.
α, beta-unsaturated carboxylic acid and acid anhydride thereof can for example be vinylformic acid, methacrylic acid, fumaric acid, Ba Dousuan, methylene-succinic acid, toxilic acid or maleic anhydride, preferred vinylformic acid.
Possible vinyl aromatic compounds for example is vinyltoluene, α-butylstyrene, 4-n-butylbenzene ethene, the positive decyl vinylbenzene of 4-, optimization styrene.
The example of nitrile is vinyl cyanide and methacrylonitrile.
The vinyl ether that is fit to for example is vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl Octyl Ether.
As non-aromatic hydrocarbon with 2-8 carbon atom and one or two olefinic double bond, can mention divinyl, isoprene, and ethene, propylene and iso-butylene.
In addition, can use N-vinyl formamide, N-vinyl pyrrolidone and N-caprolactam.
As light trigger (I), can use light trigger known in the art, for example " Advances inPolymer Science ", the 14th volume, Springer Berlin 1974 or K.K.Dietliker, Chemistry and Technology of UV-and EB-Formulation for Coatings, Inksand Paints, the 3rd volume; Photoinitiators for Free Radical and CationicPolymerization, P.K.T.Oldring (Eds), SITA Technology Ltd, those that mention among the London.
Possible light trigger for example is monoacyl phosphine oxide or two acylphosphine oxide Irgacure 819 (two (2; 4; the 6-trimethylbenzoyl) phenyl phosphine oxide); for example as described in EP-A 7508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or the EP-A 615 980; for example 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide (Lucirin TPO), ethyl-2,4, the mixture of 6-trimethylbenzoyl phenyl phosphite, benzophenone, hydroxyacetophenonum, phenyl oxoethanoic acid and derivative or these light triggers.The example that can mention is a benzophenone; methyl phenyl ketone; the acetyl naphthoquinones; butanone; the benzene pentanone; the benzene hexanone; α-phenyl phenyl propyl ketone; to the morpholine Propiophenone; dibenzosuberone; 4-morpholine benzophenone; 4-morpholine phenylbenzyl ketone; to diacetyl benzene; 4-amino-benzophenone; 4 '-methoxyacetophenone; β-Jia Jienkun; tertiary butyl anthraquinone; the anthraquinone carboxylic acids ester; phenyl aldehyde; α-Tetralone an intermediate of Sertraline; the 9-acetophenanthrene; the 2-acetophenanthrene; the 10-thioxanthone; 3-ethanoyl phenanthrene; 3-ethanoyl indoles; the 9-Fluorenone; the 1-indone; 1; 3; 4-triacetyl benzene; Thiaxanthene-9-ketone; xanthene-9-ketone; 2; 4-dimethyl thioxanthone; 2; the 4-diethyl thioxanthone; 2; 4-two-isopropyl thioxanthone; 2; 4-two-clopenthixal ketone; bitter almond oil camphor; the bitter almond oil camphor isobutyl ether; the chlorine xanthone; the bitter almond oil camphor tetrahydropyranyl ethers; benzoin methyl ether; the bitter almond oil camphor ethyl ether; the bitter almond oil camphor butyl ether; the bitter almond oil camphor isopropyl ether; the 7-H-benzoin methyl ether; benzo [taking off] anthracene-7-ketone; the 1-naphthaldehyde; 4; 4 '-two (dimethylamino) benzophenone; the 4-phenyl benzophenone; the 4-chlorobenzophenone; Michler's keton (Michler ' s ketone); the 1-acetonaphthone; the 2-acetonaphthone; 1-benzoyl basic ring-1-alcohol; 2-hydroxyl-2; the 2-dimethyl acetophenone; 2; 2-dimethoxy-2-phenyl methyl phenyl ketone; 2; 2-diethoxy-2-phenyl methyl phenyl ketone; 1; the 1-dichloroacetophenone; the 1-hydroxy acetophenone; the methyl phenyl ketone dimethyl ketal; the O-methoxy benzophenone; triphenylphosphine; the tri-o-tolyl phosphine; benzo [a] anthracene-7; the 12-diketone; 2; the 2-diethoxy acetophenone; benzyl ketals such as benzyl dimethyl ketal; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholine third-1-ketone; anthraquinone such as 2-methylanthraquinone; 2-ethyl-anthraquinone; 2-tertiary butyl anthraquinone; 1-chloroanthraquinone; 2-amyl anthraquinone and 2, the 3-dimethyl diketone.
The non-flavescence that also has the phenyl glyoxylic acid ester type that is fit to or the light trigger of slight flavescence only are as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
In the light trigger of being mentioned, preferred phosphine oxide, alpha-alcohol ketone and benzophenone.
Especially also can use the mixture of different light triggers.
Light trigger can use separately or be used in combination with for example photopolymerization promoter of phenylformic acid, amine or similar type.
As other conventional additives (J) of topcoating, can for example use antioxidant, oxidation retarder, stablizer, activator (promotor), filler, pigment, dyestuff, help air release agent, gloss-imparting agent, static inhibitor, fire retardant, thickening material, thixotropic agent, levelling agent, tackiness agent, defoamer, perfume compound, tensio-active agent, viscosity modifier, softening agent, tackifier, inner complex form agent or expanding material.
The promotor that can be used for hot after fixing for example is stannous octoate, zinc octoate, dibutyl tin laurate or diaza [2.2.2] bicyclooctane.
In addition; but can add one or more photochemistry and/or hot active initiator; Potassium Persulphate for example; dibenzoyl peroxide; cyclohexanone peroxide; two-tert-butyl peroxide; Diisopropyl azodicarboxylate; cyclohexyl alkylsulfonyl acetyl peroxide; the percarbonic acid diisopropyl ester; cross the sad tert-butyl ester or benzpinacone; and be greater than 100 hours heat-activatable initiator ditertiary butyl peroxide for example for example 80 ℃ of half-life; cumene hydroperoxide hydrogen; the diisopropyl benzene superoxide; t-butylperoxyl benzoate; trade name ADDID 600 times by the commercially available silylanizing tetramethyl ethylene ketone of Wacker; or the hydroxyl amine n-oxide is as 2; 2; 6; 6-tetramethyl piperidine-N-oxygen base; 4-hydroxyl-2; 2; 6,6-tetramethyl piperidine-N-oxygen base etc.
Other case descriptions of the initiator that is fit to are in " Polymer Handbook ", and the 2nd edition, Wiley ﹠amp; Sons is among the New York.
Spendable thickening material is free radical (being total to) polymeric (being total to) polymkeric substance and conventional organic and inorganic thickening agent such as hydroxy-methyl cellulose or wilkinite.
Form agent as inner complex, can for example use ethylenediaminetetraacetic acid and salt and beta-diketon.
The filler that is fit to comprises silicate, and for example the silicate that can obtain by the hydrolysis of silicon tetrachloride is as the Aerosil from Degussa , diatomite, talcum, pure aluminium silicate, Magnesium Silicate q-agent, Calucium Silicate powder etc.
The stablizer that is fit to comprises common UV absorption agent such as oxanilide, triazine and benzotriazole, and (latter can be used as Tinuvin The trade mark is obtained by Ciba-Spezialit  tenchemie) and benzophenone.These can use separately or with the free-radical scavengers that is fit to, for example bulky amine is as 2,2,6,6-tetramethyl piperidine, 2,6-di-t-butyl piperidines or derivatives thereof such as two-(2,2,6,6-tetramethyl--4-piperidyl) decylate use together.Stablizer is usually with based on the solid ingredient that comprises in the preparation, and the amount of 0.1-5.0 weight % is used.
Other stablizers that are fit to for example are N-oxygen base such as 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base, 4-oxo-2,2,6,6-tetramethyl piperidine-N-oxygen base, 4-acetoxyl group-2,2,6,6-tetramethyl piperidine-N-oxygen base, 2,2,6,6-tetramethyl piperidine-N-oxygen base, 4,4 ', 4 " three (2,2; 6; 6-tetramethyl piperidine-N-oxygen base) phosphite or 3-oxo-2,2,5; 5-tetramethylpyrrolidi-e-N-oxygen base; phenol and naphthols such as p-aminophenol; to quinoxin, the 2-tert-butyl phenol, the 4-tert-butyl phenol, 2,4-two-tert-butyl phenol, 2-methyl-4-tert-butyl phenol, 4-methyl-2,6-tert-butyl phenol (2, the 6-tertiary butyl-p-cresol) or the 4-tertiary butyl-2, the 6-dimethyl phenol, quinone such as quinhydrones or Hydroquinone monomethylether, aromatic amine such as N, the N-pentanoic, N nitrosodiphenyl amine, phenylenediamine such as alkyl can have 1-4 carbon atom identical or different and independently of each other and can be the N of linearity or branching, N '-dialkyl group-Ursol D, oxyamine such as N, the N-diethyl hydroxylamine, urea derivatives such as urea or thiocarbamide, P contained compound such as triphenylphosphine, triphenyl phosphite or triethyl-phosphite, or sulfocompound such as diphenyl sulfide or thiodiphenylamine.
The classical group precedent of radiation-hardenable composition is as being:
(methyl) acrylated polyolefin-wax 20-100 weight %, preferred 40-90 weight %, preferred especially 50-90 weight %, especially 60-80 weight %,
(G) 0-60 weight %, preferred 5-50 weight %, preferred especially 10-40 weight %, especially 10-30 weight %
(H) 0-50 weight %, preferred 5-40 weight %, preferred especially 6-30 weight %, especially 10-30 weight %,
(I) 0-20 weight %, preferred 0.5-15 weight %, preferred especially 1-10 weight %, especially 2-5 weight % and
(J) 0-50 weight %, preferred 2-40 weight %, preferred especially 3-30 weight %, especially 5-20 weight %,
Condition is (methyl) acrylated polyolefin-wax, (G), (H), (I) and (J) adds up to 100 weight %.
The coating of base material is undertaken by ordinary method well known by persons skilled in the art, at least a coating composition is applied on the base material to be coated with required thickness, if the suitable volatile constituent that comprises in the heat extraction coating composition that adds.If necessary, this program can repeat one or many.Being applied on the base material can be in a known way as by spraying, and by scraper, scraping blade coating, brushing, roller, curtain coating, lamination, regurgitate mist or coextrusion and apply and carry out, coat-thickness is generally about 3-1000g/m 2, preferred 10-200g/m 2
In addition, if if disclose a kind of coating composition is applied on the base material and suitable oxygen-containing atmosphere or preferably under suitable temperature under the rare gas element in drying temperature level at the most by electron beam or UV irradiation and dry, solidify, subsequently at 160 ℃ at the most, preferred 60-160 ℃ of following thermal treatment and the method for coated substrate.
The method of coated substrate also can be by at first applying the back at 160 ℃ at the most, and preferred 60-160 ℃ of following thermal treatment coating composition is subsequently at oxygen or preferably solidify by electron beam or UV irradiation under rare gas element and carry out.
If necessary, make the film that forms on the base material solidify and only to carry out with heat.Yet coating is usually by high-energy radiation irradiation and both curing of heat.
Except that thermofixation or replace thermofixation, solidify and also can be undertaken by the NIR radiation.With regard to the object of the invention, the NIR radiation is that wavelength is 760nm to 2.5 μ m, the electromagnetic radiation of preferred 900-1500nm.
If necessary, if the layered coating composition is applied over the top of each other, then heat, NIR and/or radiation curing can carry out behind each coating step.
As the source of radiation of radiation curing, can for example use Cooper-Hewitt lamp, middle medium pressure mercury lamp and high pressure mercury vapour lamp and fluorescent tube, flashlight, metal halide lamp, can be by their radiation curings without the electronic flash equipment of light trigger, or Excimer lamp.Radiation curing is UV radiation or daylight by high-energy radiation, and optimal wavelength λ=200 are to 700nm, and preferred especially λ=200 are to 500nm, and very particularly preferably λ=250 are to the effect of the light of 400nm or by using high-energy electron (electron beam; 150-300keV) irradiation and carry out.Used source of radiation for example is high pressure mercury vapour lamp, laser, flashlight (photoflash lamp), halogen lamp or Excimer lamp.Under UV solidified situation, be 80-3000mJ/cm for crosslinked usually enough radiation quantity 2
Certainly, also can use multiple as two to four kinds of source of radiation are used for solidifying.
These also can send the radiation of different wavelength range.
If suitable, irradiation also can be got rid of oxygen, for example carries out under inert atmosphere.The rare gas element preferred nitrogen, rare gas, carbonic acid gas or the combustion gases that are fit to.In addition, the available coating composition that is covered with transparent medium of irradiation carries out.Transparent medium for example is polymeric film, glass or liquid such as water.Especially preferably shine in the described mode of DE-A119957900.
The present invention further provides a kind of method of coated substrate, wherein:
I) base material is applied with aforementioned coating composition,
Ii) the volatile constituent in the coating composition is removed forming film under the condition that does not form any free radical at light trigger (I) basically as yet,
If iii) suitable, with step I i) the high-energy radiation irradiation that causes film precuring of the middle film that forms, if suitable, products machinery moulding that is coated with pre-cured film or the surface that makes pre-cured film are contacted with another kind of base material,
Iv) at last with the film thermofixation or by the NIR radiation curing.
Here step I v) and iii) also can be carried out with opposite order, promptly at first with film heat or by the NIR radiation curing, passes through high-energy radiation solidification then.
In addition, being coated with the base material of multilayer coating of the present invention also can be by the invention provides.
Coating composition of the present invention and lacquer and varnish preparaton are particularly suitable for coated substrate such as timber, paper, yarn fabric, leather, non-woven fabrics, frosting, glass, pottery, mineral construction material such as molded cement brick and asbestos cement plate, or metal, or metallizing, also can for example be the plastics or the metal of film or paper tinsel form preferably.
The described this thickness for the treatment of cured layer can for 0.1 μ m to some mm, preferred 1-2000 μ m, preferred especially 5-1000 μ m, very particularly preferably 10-500 μ m 10-250 μ m especially.
(methyl) acrylated polyolefin-wax of the present invention's preparation also can be advantageously used in thermic (free radical) (being total to) polymerization owing to their lower colors.
As for example the present invention (methyl) but the monomer of acrylated polyolefin-wax copolymerization can for example be mentioned C 1-C 20Alkyl (methyl) acrylate, has the vinyl aromatic compounds of 20 carbon atoms at the most, comprise the vinyl ester of the carboxylic acid of 20 carbon atoms at the most, olefinically unsaturated nitriles, comprise 1-10 carbon atom alcohol vinyl ether and have the aliphatic hydrocrbon of 2-8 carbon atom and 1 or 2 pair keys.
As (methyl) alkyl acrylate, preferably has C 1-C 10Those of alkyl, for example methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl propenoate and branched-alkyl derivative such as 2-EHA.
Especially the mixture of (methyl) alkyl acrylate also is suitable.
Vinyl ester with carboxylic acid of 1-20 carbon atom for example is vinyl laurate, stearic acid vinyl ester, propionate and vinyl-acetic ester.
Possible vinyl aromatic compounds for example is vinyltoluene, α-butylstyrene, 4-n-butylbenzene ethene, the positive decyl vinylbenzene of 4-, optimization styrene.
The example of nitrile is vinyl cyanide and methacrylonitrile.
The vinyl ether that is fit to for example is vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl Octyl Ether.
As non-aromatic hydrocarbon with 2-8 carbon atom and one or two olefinic double bond, can mention divinyl, isoprene, and ethene, propylene and iso-butylene.
Use always, but be not that the method for only preparation this (being total to) polymkeric substance is for free radical or ion (being total to) polymerization in solvent or thinner.
This monomeric free radical (being total to) polymerization for example at the aqueous solution at the polymerization starter that under polymerizing condition, resolves into free radical such as peracetic dithionite, H 2O 2Carry out under the existence of-redox system or hydroperoxide such as tert-butyl hydroperoxide or cumene hydroperoxide.(being total to) polymerization can be under wide temperature range, if suitable the reduction or elevated pressure carrying out under 100 ℃ usually at the most.The pH of reaction mixture is set at the value of 4-10 usually.
Yet (being total to) polymerization also can for example be carried out as solution polymerization, precipitation polymerization, water-in-oil emulsion polymerization, reverse emulsion polymerization, suspension polymerization or inverse suspension polymerization in other modes well known by persons skilled in the art continuously or in batches.
Here; monomer/multiple monomer uses radical polymerization initiator and (being total to) polymerization; described initiator is for example for to resolve into the azo-compound of free radical as 2; 2 '-azo two (isopropyl cyanide); 2; 2 '-azo two (2-amidine propane) hydrochloride or 4; 4 '-azo two-(4 '-cyanopentanoic acid); or dialkyl peroxide is as two t-amyl peroxy things; arylalkyl superoxide such as tert butyl isopropyl benzene peroxide; alkyl acyl superoxide such as t-butyl peroxy-2-ethylhexanoate, peroxy dicarbonate is as two (4-tert-butylcyclohexyl) peroxy dicarbonate or hydroperoxide.
The compound of mentioning uses with the form of the aqueous solution or aqueous emulsion usually, and concentration limit determines that by the amount of acceptable water in (being total to) polymerization upper limit of concentration is determined by the solubleness of each compound in water.
Spendable solvent or thinner for example are water, and alcohol is as methyl alcohol, ethanol, n-propyl alcohol or Virahol, propyl carbinol or isopropylcarbinol, or ketone such as acetone, ethyl methyl ketone, diethyl ketone or isobutyl methyl ketone.Preferred especially non-polar solvent such as dimethylbenzene and its isomer mixture, Shellsol A and solvent naphtha.
In preferred embodiments, with the monomer pre-mixing, if suitable initiator is added with the additive that other is dissolved in the solvent.Particularly preferred embodiment is described in WO 01/23484, and especially the 10th page, during 3-24 is capable.
If suitable, (being total to) polymerization can be carried out in the presence of polymerization regulator such as hydroxylammonium salts, chlorinated hydrocarbon and thio-compounds such as tert-butyl mercaptan, ethyl propylene acyl group mercaptoacetate, sulfydryl acetylene alcohol, sulfydryl propyl trimethoxy silicane, dodecyl mercaptans, uncle's dodecyl mercaptans or Hypophosporous Acid, 50 an alkali metal salt.In (being total to) polymerization, these conditioning agents for example can be to treat (being total to) polymerization single polymerization monomer based on 100 weight parts, and the amount of 0-0.8 weight part is used, and the molar mass of (being total to) polymkeric substance that the result forms reduces.
In letex polymerization, can use dispersion agent, ion and/or nonionic emulsifying agent and/or protective colloid or stablizer as surface active cpd.Possible such compound is GPF (General Protection False colloid and the emulsifying agent that is used to carry out letex polymerization.
The protective colloid that is fit to for example is polyvinyl alcohol, derivatived cellulose or comprises vinylpyrrolidone copolymers.The comprehensive description of the protective colloid that other are fit to can be found in Houben-Weyl, Methoden der organischen Chemie, XIV/1 volume; Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart; in 1969, the 411-420 pages or leaves.Certainly, also can use the mixture of emulsifying agent and/or protective colloid.Used dispersion agent is only preferably compared with protective colloid, and relative molecular weight is usually less than 1000 emulsifying agent.They can be for anionic, cationic or non-anionic in nature.Certainly, when using the mixture of surfactant, each component must be compatible with each other, and query can be checked by some tentative experiments in this case.Usually, anionic emulsifier is compatible with each other and compatible with nonionic emulsifying agent.
The same applies to cationic emulsifier, and negatively charged ion and cationic emulsifier are often incompatible each other.Spendable emulsifying agent for example is ethoxylation monoalkyl phenol, dialkyl phenol and trialkyl phenol (EO content: 3-100, alkyl: C 4-C 12), ethoxylized fatty alcohol (EO content: 3-100, alkyl: C 8-C 18), and alkyl sodium sulfate ester (alkyl: C 8-C 16), sulfuric acid monoester (EO content: 3-100, the alkyl: C of ethoxylated alkylphenol 4-C 12), alkylsulphonic acid (alkyl: C 12-C 18) and alkyl acryl sulfonic acid (alkyl: C 9-C 18) an alkali metal salt and ammonium salt.Other emulsifying agent such as sulfosuccinic esters that are fit to can be found in Houben-Weyl, Methoden der organischen Chemie, XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme Verlag, Stuttgart, in 1961, the 192-208 pages or leaves.
Usually, the consumption of dispersion agent is based on the monomer for the treatment of radical polymerization, 0.5-6 weight %, preferred 1-3 weight %.
The example that contains the dispersion of (methyl) acrylate is the n-butyl acrylate/vinyl cyanide dispersion that can be used as tackiness agent, n-butyl acrylate/Butadiene dispersion.
Can the polymeric dispersions chemistry and/or the physical deodorization of the present invention's (methyl) acrylated polyolefin-wax will be used extraly.
Use the available multipolymer of the present invention's (methyl) acrylated polyolefin-wax to have lower colour usually, this is favourable in the topcoating field.Described multipolymer then can be in a manner known way for example with aminoplastics such as trimeric cyanamide reaction to obtain crosslinked coating resin, for example as described in EP 738740 or the EP 675141.
Coating composition of the present invention especially is suitable as exterior coating or coating externally, and promptly they are exposed under the daylight in application, are preferred for buildings or partial building, coated inside, and road markings uses in the coating on vehicle or the flyer.Coating especially as timber, paper or plastic coating, for example is used for parquet floor or furniture.
Following embodiment is used to illustrate and unrestricted the present invention.
Embodiment
Except as otherwise noted, in this article, " part " is " weight part ".
Abbreviation:
HBVE: hydroxybutyl vinyl ether
HEMA: methacrylic acid hydroxyl ethyl ester
E: ethene
Novozym 435: from the fixed fat enzyme of antarctic candida Type B (from Novozymes, Denmark)
Embodiment 1: the acrylated poly-(ethene-be total to-the hydroxybutyl vinyl ether) that comprises 4.9 moles of %HBVE
Figure A20068000670700411
In the 1l four neck flasks that are equipped with stacked precision glass agitator and reflux exchanger, poly-(ethene-altogether-HBVE), 500ml hexanaphthene, 50.0g methyl acrylate (580 mmole), the 5.0gNovozym that 100.0g are comprised 4.9 moles of %HBVE (OH number: 86mg/g is equivalent to 154 mmole OH) 435 and 20.0g molecular sieve (5 ) stirred 24 hours down at 60 ℃.Muddy micro white solution washs with hexanaphthene by the suction filter heat filtering and with the residue on the strainer.Filtrate is being evaporated to drying on the rotary evaporator under 60 ℃/6 millibars.This obtains 112.3g corresponding to 72% OH acrylated degree, and the OH number is the colourless wax of 24mg/g.
Embodiment 2: the acrylated poly-(ethene-be total to-the hydroxybutyl vinyl ether) that comprises 2.9-4.9 mole %HBVE
With 5.0g poly-(ethene-be total to-HBVE) (see Table), 5.0g methyl acrylate, 50ml solvent (toluene, hexanaphthene or methyl acrylate; See Table), 3.0g molecular sieve (5 ) and 500mgNovozym 435 rocked under 40 ℃ 24 hours in the bottle of screw-top.Filtering the acrylated degree of back OH measures by the OH number.
The HBVE content of polymkeric substance Acrylated degree [%]
[mole %] Toluene Hexanaphthene Methyl acrylate
2.9 61 68 52
3.8 70 74 54
4.9 80 85 71
Embodiment 3: the acrylated poly-(ethene-be total to-the hydroxybutyl vinyl ether) that comprises 2.9 moles of %HBVE
5.0g is comprised 2.9 moles of %HBVE (being equivalent to 5.0 mmole OH) poly-, and (ethene-altogether-HBVE), 5.0g methyl acrylate (58 mmole), 50ml hexanaphthene, 3.0g molecular sieve 5  and 500mg enzyme rocked in water-bath under 40 ℃ 24 hours in the bottle of screw-top.Filtering the acrylated degree of back OH measures by the OH number.
Immobilized enzyme Acrylated degree [%]
Lipase from the antarctic candida Type B 68
Lipase from the Burkholder Pseudomonas 54
Immobilized lipase (lipozyme) from the conspicuous Mucor (Mucor miehei) of rice 50
From the immobilized lipase of dredging cotton shape thermophilic fungus (Thermomyces lanuginose) 39
Lipase from Alkaligenes 38
Lipase from achromobacter (Achromobacter sp.) 29
Lipase from antarctic candida A type 27
Subtilisin from Bacillus licheniformis (Bacillus licheniformis) 13
Embodiment 4: the acrylated poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester) that comprises 10.7 moles of %HEMA
A) preparation poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester)
Preparation poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester) is by making ethene and HEMA radical polymerization in the 1 liter of autoclave that stirs.
For this reason, at first 12kg/h ethene is compressed to 260 crust with successive processes in first compressor.The solution of 3.71l/h HEMA and toluene (1: 1) and the propionic aldehyde that 2.4l/h sets required viscosity as conditioning agent are infeeded intermediate pressure zone.In second compressor, this mixture is compressed to 1700 crust and infeeds autoclave.Polymerization causes by add equally the solution of peroxide PIVALIC ACID CRUDE (25) tertiary butyl ester in Permethyl 99A. that infeeds in the autoclave by high-pressure pump independently under 1700 crust.Polymerization temperature is 220 ℃.Viscosity (the dynamic fusion viscosity under 120 ℃) is 60mm 2/ s, molar mass M wBe 1005g/mol (M w/ M n=2.75) ethylene copolymer obtains with the output of 4.2kg/h.Molar mass distribution does not show the crosslinked of OH and ester group.
According to 1H-NMR, the ethene that consists of 89.1 moles of % (63.8 weight %) copolymerization of ethylene copolymer and the HEMA of 10.7 moles of % (35.7 weight %) copolymerization.Can detect the remaining HEMA monomer content of 0.2 mole of %.Conversion of ethylene is 22%, and the HEMA transformation efficiency is 76%.
B) acrylated of poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester)
Figure A20068000670700431
In the 500ml four neck flasks that are equipped with stacked precision glass agitator and reflux exchanger, poly-(ethene-altogether-HEMA), 60.0g methyl acrylate (700 mmole), 12mg Hydroquinone monomethylether (200ppm), the 6.0gNovozym that 100.0g are comprised 10.7 moles of %HEMA (OH number: 158mg/g is equivalent to 282 mmole OH) 435 and 60.0g molecular sieve powder (5 ) stirred 8 or 24 hours down at 60 ℃.The little white solution of muddiness is filtered helping with the 300ml dilution with toluene, enzyme is leached and use toluene wash on filtration device.Filtrate is being evaporated to drying on the rotary evaporator under 60 ℃/6 millibars.This obtains measuring by the OH number colourless wax of its acrylated degree.
Experiment numbers Reaction times Initial OH number [mg/g] Final OH number [mg/g] Transformation efficiency [%] Product weight [g]
1 8 hours 160 6 96 107
2 24 hours 160 7 96 108
Embodiment 5: the acrylated that comprises 7.9 moles of %HEMA of different molar masss poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester)
Polymkeric substance 1: comprise 28.5 weight % (=7.9 moles of %) HEMA poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester), the OH number: 123mg KOH/g, 120 ℃ of following viscosity are 60mPas
Polymkeric substance 2: comprise 28.5 weight % (=7.9 moles of %) HEMA poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester), the OH number: 123mg KOH/g, 120 ℃ of following viscosity are 1030mPas
Polymkeric substance 2 has same composition but shows that by higher viscosity molar mass is higher than polymkeric substance 1.
With 5.0g polymkeric substance 1 or 2 (10.98 mmole OH), 3.0g methyl acrylate (15.38 mmole), 10ml toluene, 100mgNovozym 435 and 3.0g molecular sieve spheres 5  screw-top the bottle under 60 ℃, in water-bath, rocked 1,6 or 24 hour.Sample is filtered, remove under the pressure that reduces and desolvate and excessive propene acid methyl esters, product characterizes and measures the acrylated degree by H-NMR.
Reaction times Acrylated degree [%]
Polymkeric substance 1 Polymkeric substance 2
24 hours 49 66
6 hours 33 43
6 hours, catalyst-free 0 0
1 hour 23 20
Embodiment 6: the acrylated poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester) (distillating method) that comprises 9.9 moles of %HEMA
Polymkeric substance 3: comprise 33.6 weight % (=9.99 moles of %) HEMA poly-(ethene-be total to-methacrylic acid hydroxyl ethyl ester), the OH number: 151mg KOH/g, 120 ℃ of following viscosity are 60mPas
In round-bottomed flask, with 20.0g polymkeric substance 3 (53.8 mmole OH), 80 or 160g methyl acrylate (929 mmole), 1.0gNovozym 435, the pressure of specified below temperature of 20mg Hydroquinone monomethylether and 20mg butylated hydroxy anisole and reduction stirred 8 hours down.The azeotropic steam mixture of methyl alcohol and methyl acrylate reaches reflux exchanger and condensation via Glass tubing.Condensation product drops in 30g and can absorb on molecular sieve 5  of methyl alcohol, gets back in the reaction soln.
Sample is filtered, and product characterizes and measures the acrylated degree by H-NMR.
The pressure of temperature/reduction Methyl acrylate Transformation efficiency
55℃ 80g 83％
40℃ 160g 70％
40℃ 80g 71％

Claims (15)

1. comprise (methyl) acrylated polyolefin-wax that component is formed in following copolymerization with polymerized form under formal every kind of situation:
A) at least a alkene that does not have other functional groups,
B1) at least a alkenyloxy alkyl (methyl) acrylate and/or allyloxy alkyl (methyl) acrylate
And/or
B2) at least a (methyl) acryloxyalkyl (methyl) acrylate and/or (methyl) acryloxyalkyl (methyl) acrylamide and
C) if suitable, at least aly be different from a), b1) and b2) and have a monomer of at least one functional group.
2. according to the polyolefin-wax of claim 1, wherein said Olefin) be selected from ethene, propylene, 1-butylene, 2-butylene, iso-butylene, 1-amylene, 2-amylene, 1-hexene, 1-octene, number-average molecular weight M nBe the daltonian polyisobutene of 100-1000, cyclopentenes, tetrahydrobenzene, divinyl, isoprene and vinylbenzene.
3. according to each polyolefin-wax in the aforementioned claim, wherein said monomer b1) be alkenyloxy alkyl (methyl) acrylate and/or allyloxy alkyl (methyl) acrylate of a kind of formula (II):
Figure A2006800067070002C1
Or
Wherein
R 2And R 4Be hydrogen or methyl separately independently of each other,
R 3For optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 2-C 20Alkylidene group, C 5-C 12Cycloalkylidene or C 6-C 12Arylidene or at interval one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-and/or one or more cycloalkyl ,-(CO)-,-O (CO) O-,-(NH) (CO) O-,-O (CO) (NH)-,-O (CO)-or-(CO) C of O- 2-C 20Alkylidene group.
4. according to each polyolefin-wax in the aforementioned claim, wherein said monomer b2) be (methyl) acryloxyalkyl (methyl) acrylate of formula (III):
Figure A2006800067070003C1
Or (methyl) acryloxyalkyl (methyl) acrylamide of formula (IIIa):
Figure A2006800067070003C2
Wherein
R 5And R 7Be hydrogen or methyl separately independently of each other, and
R 6For optional aryl replaces, alkyl replaces, aryloxy replaces, alkoxyl group replaces, heteroatoms replaces and/or the C of heterocyclic substituted 1-C 20Alkylidene group, C 5-C 12Cycloalkylidene or C 6-C 12Arylidene or at interval one or more oxygen and/or sulphur atom and/or one or more replacement or unsubstituted imino-and/or one or more cycloalkyl ,-(CO)-,-O (CO) O-,-(NH) (CO) O-,-O (CO) (NH)-,-O (CO)-or-(CO) C of O- 2-C 20Alkylidene group.
5. according to each polyolefin-wax in the aforementioned claim, wherein said monomer c) be selected from (methyl) vinylformic acid C 1-C 20Alkyl ester comprises the vinyl acetate of the carboxylic acid of 20 carbon atoms at the most, and olefinically unsaturated nitriles comprises the vinyl ether of the alcohol of 1-10 carbon atom, and α, beta-unsaturated carboxylic acid and acid anhydride thereof.
6. method for preparing (methyl) acrylated polyolefin-wax, it may further comprise the steps:
(1) prepare polyolefin-wax by following monomer copolymerization:
A) at least a alkene that does not have other functional groups,
B1) at least a hydroxyalkyl alkenyl ether and/or hydroxyalkyl allyl ethers and/or
B2) at least a hydroxyalkyl (methyl) acrylate and/or hydroxyalkyl (methyl) acrylamide and
C) if suitable, at least a A of being different from), B1) and B2) and have a monomer of at least one functional group,
(2) if suitable, the polyolefin-wax that obtains is purified,
(3) polyolefin-wax that will obtain by (1) or (2) with (methyl) acroleic acid esterification and/or with the transesterify of (methyl) acrylate,
(4) if suitable, (methyl) acrylated polyolefin-wax that obtains is purified.
7. according to the method for claim 6, wherein said monomers B 1) be the hydroxyalkyl alkenyl ether or the hydroxyalkyl allyl ethers of formula (IV):
Figure A2006800067070004C1
Or
R wherein 2And R 3As defined in claim 3.
8. according to the method for claim 6, wherein said monomers B 2) be hydroxyalkyl (methyl) acrylate or hydroxyalkyl (methyl) acrylamide of formula V:
Figure A2006800067070004C3
Or
Figure A2006800067070004C4
R wherein 5And R 6As defined in claim 4.
9. according to each method among the claim 6-8, wherein said esterification is being carried out under 60-140 ℃ in the presence of esterifying catalyst and at least a stopper, and the reaction times is 3-20 hour.
10. according to each method among the claim 6-8, at least a C is used in wherein said transesterify in the presence of at least a transesterification catalyst 1-C 10Alkyl (methyl) acrylate carries out under 80-140 ℃ temperature of reaction, and the reaction times is 1-4 hour.
11. according to each method among the claim 6-8, wherein said esterification or transesterify are carried out in the presence of at least a enzyme.
12., wherein make 10-80% be contained in hydroxy functional group esterification or transesterify in the polyolefin-wax that has hydroxyalkyl according to each method among the claim 9-11.
13., wherein make at least 80% hydroxy functional group esterification or the transesterify that is contained in the polyolefin-wax that has hydroxyalkyl according to each method among the claim 9-11.
14. be used for the dispersing of pigments agent according to each polyolefin-wax conduct among the claim 1-5, lubricant, be particularly useful for the PVC polymkeric substance, the matting agent that is used for topcoating, the tensio-active agent that is used for printing-ink, leather coating, textile coating or the purposes in radiation-hardenable and/or heat-setting coating composition.
15. comprise the coating composition that adds following component according to each (methyl) acrylated polyolefin-wax among the claim 1-5:
(G) but at least a polymerizable compound with a plurality of copolymerization ethylenically unsaturated groups,
(H) if suitable, reactive thinner,
(I) if suitable, light trigger and
(J) if suitable, the additive of other conventional topcoatings.
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ES2337393T3 (en) 2010-04-23
US20080249204A1 (en) 2008-10-09
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DE102005010109A1 (en) 2006-09-07
US7714038B2 (en) 2010-05-11
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EP1856166B1 (en) 2009-12-16

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